Coating line and process for forming a multilayer component coating on a substrate

ABSTRACT

A process for forming a multilayer composite coating on a substrate is provided. The process includes forming an electrodeposition coating layer on the substrate by electrodeposition of a curable electrodepositable coating composition over at least a portion of the substrate. Optionally, the coated substrate is heated to a temperature and for a time sufficient to cure the electrodeposition coating layer. A basecoating layer is formed on the electrodeposition coating layer by depositing an aqueous curable basecoating composition directly onto at least a portion of the electrodeposition coating layer. Optionally, the basecoating layer is dehydrated. A top coating layer is formed on the basecoating layer by depositing a curable top coating composition which is substantially pigment-free directly onto at least a portion of the basecoating layer. The top coating layer, the basecoating layer, and, optionally, the electrodeposition coating layer are cured simultaneously.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.12/394,086 filed Feb. 27, 2009 which is a divisional of U.S. patentapplication Ser. No. 10/366,222 filed Feb. 13, 2003 which claims thebenefit of U.S. Provisional Patent Application Ser. No. 60/356,520 filedFeb. 13, 2002.

FIELD OF THE INVENTION

The present invention relates to a process for forming a multilayercomposite coating on a substrate, particularly an automotive vehiclesubstrate, and a coating line wherein the process is employed.

BACKGROUND OF THE INVENTION

Multilayer composite coatings, for example, color-plus-clear coatingsystems, involving the application of a colored or pigmented basecoat toa substrate followed by application of a transparent or clearcoat overthe basecoat, have become increasingly popular as original finishes fora number of consumer products including, for example, automotivevehicles. The color-plus-clear coating systems have outstandingappearance properties such as gloss and distinctness of image, andprovide excellent coating systems such as corrosion resistance, scratchand abrasion resistance, and resistance to deleterious environmentalconditions such as acid rain. Such color-plus-clear coating systems havebecome popular for use on automotive vehicles, aerospace substrates,floor coverings such as ceramic tiles and wood flooring, packagingmaterials and the like

A conventional automotive coating process typically includes thesequential application of an electrodepositable coating composition,usually a cationic composition, a primer-surfacer coating compositionover the electrodeposition coating, a color-enhancing and/oreffect-enhancing basecoating composition over the primer-surfacercoating, and a transparent or clear coating composition over thebasecoat. In some instances, the electrodeposition coating is appliedover a mill-applied weldable, thermosetting coating which has beenapplied to the coiled steel metal substrate from which the autobody (orautobody parts, such as fenders, doors, and hoods) are formed.

For example, as mentioned above, on most automotive coating lines, theauto body is first given an electrodeposition coating commonly formedfrom a cationic electrodepositable coating composition. Thiselectrodeposition coating typically is then thermally cured. Theelectrodeposition coating must be fully adherent to the substrate andinhibits corrosion of the substrate to which it is applied. Inconventional electrodeposition coatings, the excellent adhesion andcorrosion resistance properties can be derived from the inclusion in theelectrodepositable composition of ionic film-forming resins and/orcrosslinking agents which can comprise aromatic moieties. Whileproviding excellent adhesion and corrosion resistance, these resinsand/or crosslinking agents can be susceptible to degradation by visibleand/or ultraviolet light which can penetrate through the subsequentlyapplied coating layers. Such photodegradation can result in delaminationof the electrodeposition coating from the substrate, causingcatastrophic failure of the multilayer composite coating system.

A primer-surfacer coating composition typically is applied to the curedelectrodeposition coating, and the primer-surfacer coating is thenthermally cured. The primer-surfacer coating composition usuallycomprises a polymer composition which provides a tough and flexiblecoating; and typically is heavily pigmented, for example, with fillerpigments, such as talc and clay, and often containsphotodegradation-resistant pigments, for example, carbon black. Thecured primer-surfacer coating layer can have a film thickness as high as100 micrometers, but usually between 25 and 50 micrometers. As such, theprimer-surfacer coating can enhance chip resistance of the multilayercomposite coating system, and also can mask any surface defects presentin the electrodeposition coating, thereby ensuring a smooth appearanceof the subsequently applied top coatings. Moreover, the primer-surfaceraffords visible and ultraviolet light opacity to preventphotodegradation of the previously applied electrodeposition coating.One known primer-surfacer is GPX 45379 commercially available from PPGIndustries, Inc. of Pittsburgh, Pa.

A basecoating composition, most often an aqueous composition, then isapplied to the cured primer-surfacer coating. The basecoatingcomposition usually contains color-enhancing and/or effect-enhancingpigments.

The basecoating is typically given a flash bake at a temperature and fora time sufficient to drive off excess solvents, but insufficient to curethe basecoating composition. A transparent or clear coating then isapplied to the uncured basecoating. This is commonly referred to as awet-on-wet application. The clear coat can provide excellent gloss anddistinctive of image, as well as scratch and mar resistance, andresistance to harsh environmental conditions.

In one known coating line, the substrate is electrocoated at anelectrocoating station and then is moved into a primer zone forapplication of the primer-surfacer. As described above, theprimer-surfacer is typically a relatively thick coating to mask surfacedefects in the underlying substrate. The applied primer-surfacer layeris cured and then the cured primer-surfacer can be sanded to removesurface defects and to provide a smooth outer surface for theapplication of further coatings. However, this sanding process canresult in small particles of grit or dirt that must then be brushed ortacked off of the substrate before further coatings can be applied.After this tacking process, the substrate is moved into a basecoatingzone where the fully color-pigmented basecoat composition is appliedonto the cut-in portions of the substrate. The same fullycolor-pigmented basecoat composition is applied onto the primer-surfacerover the exterior of the substrate at one or more subsequent basecoatstations. The applied basecoat compositions are then baked to pre-drythe basecoating, and a clearcoat composition is applied onto thebasecoat on the substrate exterior. Typically, the clearcoat compositionis not applied onto the basecoat in some areas in the cut-in portions.

Due to the resultant cost-savings, there has been recent interest in theautomotive coatings market in reducing the cured film thickness of oneor more of the coating layers in the multilayer composition coating,and/or eliminating one or more of the coating steps altogether. Forexample, in some multilayer coating processes the primer-surfacercoating application and curing steps can be eliminated. That is, thebasecoating composition is applied directly onto the curedelectrodeposition coating. In such modified coating processes, both theelectrodeposition coating and the basecoating are required to meetstringent durability, appearance, and physical propertiesspecifications.

Further, as previously mentioned, for some applications, a weldable,corrosion inhibitive primer coating is mill-applied to metallicsubstrates. The basecoating composition can then be applied directly tothe cured weldable primer coating with no intervening electrodepositioncoating and no primer-surfacer coating.

Also, automotive parts and accessories, for example non-metal orelastomeric autobody parts, such as bumpers and body side moldings,typically are coated “off site” and shipped to the automobile assembleplants. Such substrates do not require corrosion resistance as do themetallic substrates discussed above. Hence, the basecoating compositioncan be applied directly to the non-metal substrate surface, or,alternatively, to a previously applied intervening adhesion-promotingprimer coating.

U.S. Pat. No. 6,221,949 B1 discloses a coating formulation for use inmulticoat paint systems which comprises a water-dilutable polyurethaneresin having an acid number of 10 to 60 and a number average molecularweight of 4000 to 25,000. The polyurethane is prepared by reacting apolyester and/or polyether polyol having a number average molecularweight of 400 to 5000 or a mixture of such polyesters and polyetherpolyols; a polyisocyanate or mixture thereof; a compound which has inthe molecule at least one group reactive toward isocyanate groups and atleast one group capable of forming anions or a mixture of suchcompounds; and optionally a hydroxyl and/or amino-containing organiccompound having a molecular weight of from 40 to 400, and at leastpartially neutralizing the resulting reaction product. The compositionfurther comprises pigments and/or fillers where the ratio of binder topigment is between 0.5:1 to 1.5:1. In such compositions, the presence oftalc is required in an amount of 20 to 80% by weight of the overallquantity of pigment. This composition is employed in a process forforming a multicoat paint system in which the substrate is coated withan electrodeposition coating which is optionally predried or baked, thecomposition described above is applied to the electrodeposition coatingand optionally predried without baking, a second aqueous coating isapplied to the coating formed from the previously described compositionand optionally predried without baking, a transparent coating is appliedto the coating formed from the second aqueous composition, and theoverall paint system is baked.

U.S. Pat. No. 5,976,343 discloses a process for multicoat lacquering ofa substrate with a stoved first electrodeposition layer by a applying asecond surface coating layer having a dry thickness of 10 to 30 micronsconsisting of a base lacquering agent containing a first water-basedpolyurethane resin, and wet-on-wet application of a third coating agentwith a dry layer thickness of 7 to 15 microns. The third coating layerconsists of a second water-based lacquering agent containing apolyurethane resin. A clear lacquering layer is then applied withoutstoving of the third coating agent, and the multicoat system is stovedto mutually cure the second, third and clear lacquer layers. The firstbase lacquering agent has a higher concentration of polyurethane resinthan does the second base lacquering agent. Further, the patentdiscloses that the first base lacquering agent is prepared from thesecond base lacquering agent by admixing an appropriate amount ofpolyurethane resin with the second base lacquering agent.

U.S. Pat. No. 4,820,555 discloses a method for forming a multicoatsystem on a substrate by first applying an electrocoating composition toa substrate and curing the electrocoating composition, applying asealercoating composition over the electrocoat and, optionally, bakingthe sealercoating, applying a metallic basecoating composition over thesealercoating, either drying, flash-baking, or curing the metallicbasecoating, applying a clearcoating composition over the metallicbasecoating, and baking the multicoat system. The sealercoatingcomposition can be solvent-based or water-based, and provides improvedmetallic pigment orientation, basecoat smoothness and adhesion.

In an attempt to alleviate some of the problems associated with knowncoating processes, another coating line has been developed in whichprimer-surfacer application has been eliminated. However, in thisprocess the structure and operation of the coating line must besignificantly altered in order to accommodate problems arising from thischange. For example, in this process after application of theelectrodeposition coating, a first basecoat composition is applied overthe exterior surface of the substrate. This first basecoat compositionis a chip resistant, color pigmented composition that can be color keyedto approximate the desired final color of the coated substrate. Thefirst basecoat composition is then heated to pre-dry the first basecoatand a second basecoat composition of the desired final colorpigmentation is applied onto the first basecoat composition on theexterior surface. The cut-in portions are coated with the secondbasecoat composition, between application of the first and secondbasecoating composition. This modification is required due to the colortransition areas that would be visible if the cut-in portions werecoated first, as in a typical coating process. However, this change inthe coating sequence means that this process is not easily incorporatedin existing coating lines that are set up to coat the cut-in portions ofthe substrate before the exterior portions. Added expense must beincurred to either build a new coating line to practice this process orto modify an existing line to move the cut-in application to the end ofthe basecoating zone.

In view of the foregoing, it would be advantageous to provide a processfor forming a multilayer composite coating system which eliminates theapplication and curing of a primer-surfacer coating whereby a firstbasecoating composition can be applied directly to an electrodepositioncoating, or, alternatively, to a treated or untreated substrate;followed by wet-on-wet application of a second color- oreffect-enhancing basecoat, the composition of which can be the same ordifferent from that of the first basecoating composition, withsubsequent wet-on-wet application of a clearcoat. Further, it isdesirable that such a multilayer composite coating system be applied ona conventional coating line without significant modification.

SUMMARY OF THE INVENTION

A process for forming a multilayer composite coating on a substrate, theprocess comprising: forming a first basecoating layer on the substrateby depositing an aqueous curable first basecoating composition over atleast a portion of the substrate with no intervening primer-surfacerlayer, optionally, dehydrating the first basecoating layer; forming asecond basecoating layer on the first basecoating layer by depositing anaqueous curable second basecoating composition, which is the same ordifferent from the first basecoating composition, directly onto at leasta portion of the first basecoating layer, optionally, dehydrating thesecond basecoating layer; forming a top coating layer on the secondbasecoating layer by depositing a curable top coating composition whichis substantially pigment-free directly onto at least a portion of thesecond basecoating layer; and curing the top coating layer, the secondbasecoating layer, and the first basecoating layer simultaneously.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic block diagram (not to scale) of a coating systemincorporating features of the present invention; and

FIG. 2 is a schematic block diagram (not to scale) of a basecoat zone ofanother embodiment of a coating system incorporating features of thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, spatial or directional terms, such as “inner”, “outer”,“left”, “right”, “up”, “down”, “horizontal”, “vertical”, and the like,relate to the invention as it is shown in the drawing figure. However,it is to be understood that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting. Also, as used herein, the terms “deposited over”, “appliedover”, or “provided over” mean deposited, applied, or provided on, butnot necessarily in surface contact with. For example, a material“deposited over” a substrate does not preclude the presence of one ormore other materials of the same or different composition locatedbetween the deposited material and the substrate. Additionally, theterms “upstream” and “downstream” refer to the direction of movement ofa substrate in the described coating process.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions and soforth used in the specification and claims are to be understood as beingmodified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical values, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of 1″ to 10″ is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10.

Also, as used herein, the term “polymer” is meant to refer to oligomersand both homopolymers and copolymers. Unless stated otherwise, as usedin the specification and the claims, molecular weights are numberaverage molecular weights for polymeric materials indicated as “Mn” andobtained by gel permeation chromatography using polystyrene standards inan art-recognized manner.

Before describing in detail an exemplary practice of the invention, anexemplary coating line (coating system) incorporating features of theinvention will be briefly described.

FIG. 1 schematically depicts a coating system 10 incorporating featuresof the invention. This system 10 is suitable for coating substrates,e.g., metal or polymeric substrates, in a batch or continuous process.In a batch process, the substrate is stationary during each treatmentstep whereas in a continuous process the substrate is in continuousmovement along the coating line. An exemplary process of the inventionwill be discussed first in the context of coating a substrate in acontinuous coating line.

Useful substrates that can be coated according to the method of thepresent invention include metallic substrates, polymeric substrates,such as thermoset materials and thermoplastic materials, andcombinations thereof. The substrates can be used as components tofabricate automotive vehicles, including but not limited to automobiles,trucks and tractors. The substrates can have any shape, but in oneembodiment are in the form of automotive body components such as bodies(frames), hoods, doors, fenders, bumpers and/or trim for automotivevehicles.

With reference to FIG. 1, a metal substrate 12 can be cleaned anddegreased at a pretreatment zone 14. A pretreatment coating, such asCHEMFOS 700® zinc phosphate or BONAZINC® zinc-rich pretreatment (eachcommercially available from PPG Industries, Inc. of Pittsburgh, Pa.),can be deposited over the surface of the metal substrate 12.

Alternatively or additionally, one or more optional electrodepositioncoating compositions can be electrodeposited over at least a portion ofthe metal substrate 12 at an optional electrodeposition zone 16. Onesuitable electrodeposition coating is POWER PRIME® coating commerciallyavailable from PPG Industries, Inc. of Pittsburgh, Pa. Usefulelectrodeposition methods and electrodeposition coating compositionsinclude conventional anionic or cationic electrodepositable coatingcompositions, such as epoxy or polyurethane-based coatings. Suitableelectrodepositable coatings are discussed in U.S. Pat. Nos. 4,933,056;5,530,043; 5,760,107 and 5,820,987, which are incorporated herein byreference. The optional electrodeposition coating can be optionallydried or cured in a drying device, such as an oven 18, before furtherprocessing. Alternatively, additional coatings as described below can beapplied wet-on-wet over the electrodeposition coating.

Unlike conventional coating lines, the coating line of the inventiondoes not include a primer-surfacer zone for application, curing, and/orsanding of a primer-surfacer. By eliminating the need for aprimer-surfacer, the coating equipment required for primer-surfacerapplication, e.g., coating booths, coating applicators, drying ovens,sanding equipment, and tacking equipment, can also be eliminated.Additionally, the elimination of the primer-surfacer also speeds up theoverall coating process and reduces the floor space needed to coat thesubstrate 12.

A multi-layer basecoat can be applied over the substrate 12 in amulti-step method at a basecoat zone 20 comprising one or more coatingstations. The basecoat zone 20 can be located downstream of and/oradjacent to the electrodeposition zone 16. As used herein, the term“adjacent to” means that there are no intervening coating stations ormajor processing stations located between the adjacent stations. In theembodiment shown in FIG. 1, the substrate 12 is conveyed into a cut-instation 22 having one or more conventional coating applicators 24, suchas conventional bell or gun applicators. As will be appreciated by oneof ordinary skill in the automotive coating art, bell applicatorstypically include a body portion or bell having a rotating cup. The bellis connected to a high voltage source to provide an electrostatic fieldbetween the bell and the substrate. The electrostatic field shapes thecharged, atomized coating material discharged from the bell into acone-shaped pattern, the shape of which can be varied by shaping airejected from a shaping air ring on the bell. Non-limiting examples ofsuitable conventional bell applicators include Eco-Bell or Eco-M Bellapplicators commercially available from Behr Systems Inc. of AuburnHills, Mich.; Meta-Bell applicators commercially available fromABB/Ransburg Japan Limited of Tokyo, Japan; G-1 Bell applicatorscommercially available from ABB Flexible Automation of Auburn Hills,Mich.; or Sames PPH 605 or 607 applicators commercially available fromSames of Livonia, Mich.; or the like.

The applicators 24 are connected to and are in flow communication with asource 26 of a basecoat composition. In one embodiment, the basecoatcomposition in the source 26 is the “second basecoat composition”described in detail below. In another embodiment, the source 26 includesan admixture of the “first and second basecoat compositions” describedbelow. In the cut-in station 22, the basecoat composition from thesource 26 is applied over the cut-in portions of the substrate 12. Aswill be appreciated by one of ordinary skill in the automotive coatingart, the term “cut-in portions” refers to those areas of the substratethat are not normally subjected to exposure to corrosive atmosphericconditions. Examples of cut-in portions include the interior door jams,the inside of the trunk lid, etc. An optional drying device, such as anoven 28 or flash chamber, can be located downstream of and/or adjacentto the cut-in station 22 to optionally flash, dry, or cure the coatingapplied over the cut-in portions before further coating.

After the cut-in station 22, the substrate 12 can be conveyed into anadjacent first basecoat station 30 having one or more conventionalapplicators 32, e.g., bell or gun applicators, connected to or in flowcommunication with a source 34 of a first basecoat material orcomposition as described in more detail below. The first basecoatcomposition can be applied, e.g., sprayed, over the substrate 12 by oneor more applicators 32 at the first basecoat station 30 in one or morespray passes to form a first basecoat layer over the substrate 12. Aswill be described in more detail below, the first basecoat compositionincludes a first resinous binder and a first pigment compositioncomprising one or more pigments dispersed in the first resinous binder.

An optional drying device, such as an oven 36 or flash chamber, can belocated downstream of and/or adjacent to the first basecoat station 30to optionally flash, dry, or cure the coating applied at the firstbasecoat station 30 (and optionally the coating applied over the cut-inportions) before further coating. The temperature and humidity in thedrying device can be controlled to control evaporation from thedeposited first basecoat composition to form a first basecoat layer withsufficient moisture content or “wetness” such that a substantiallysmooth, substantially level film of substantially uniform thickness isobtained without sagging. In one embodiment, there is no dehydration ofthe applied first basecoat composition before application of the secondbasecoat composition described below.

A second basecoat station 40 can be located downstream of and/oradjacent to the first basecoat station 30 and can have one or moreconventional applicators 42, e.g., bell or gun applicators, connected toand in flow communication with a source 46 of a second basecoatcomposition as described in more detail below. The second basecoatcomposition can be applied, e.g., sprayed, over the first basecoatcomposition by one or more applicators 42 at the second basecoat station40 in one or more spray passes to form a second basecoat layer over thefirst basecoat layer. In one embodiment, the second basecoat compositionis applied “wet-on-wet” onto the first basecoat composition, i.e., thereis no dehydration of the applied first basecoat composition beforeapplication of the second basecoat composition. Thus, a multilayercomposite basecoat can be formed by one or more second basecoat layersapplied over one or more first basecoat layers. As used herein, theterms “layer” or “layers” refer to general coating regions or areaswhich can be applied by one or more spray passes but do not necessarilymean that there is a distinct or abrupt interface between adjacentlayers, i.e., there can be some migration of components between thefirst and second basecoat layers. As described in more detail below, thesecond basecoat composition includes a second resinous binder that canbe the same or different than the first resinous binder. The secondbasecoat composition also includes a second pigment composition that canbe the same as or different than the first pigment composition.

A conventional drying device, such as an oven 50, can be locateddownstream of and/or adjacent to the second coating station 40 where thecoating(s) applied at the cut-in station 22, and/or the first basecoatstation 30, and/or the second basecoat station 40 can be dried or cured.For waterborne basecoats, “dry” means the almost complete absence ofwater from the applied compositions. Drying the basecoat enablesapplication of a subsequent protective topcoat or clearcoat, asdescribed below, such that the quality of the clearcoat will not beadversely affected by further drying of the basecoat. If too much wateris present in the basecoat, the subsequently applied clearcoat cancrack, bubble or “pop” during drying of the clearcoat as water vaporfrom the basecoat attempts to pass through the clearcoat. The oven 50can be a conventional drying oven or drying apparatus, such as aninfrared radiation oven commercially available from BGK-ITW AutomotiveGroup of Minneapolis, Minn.

After the basecoat compositions on the substrate 12 have been optionallydried (and cured and/or cooled, if desired) in the oven 50, one or moreconventional clearcoats or topcoats can be applied over the basecoat ata clearcoat zone 52 comprising one or more clearcoat stations 54. Eachclearcoat station includes one or more conventional applicators 56(e.g., bell applicators) connected to and in flow communication with asource 58 of clearcoat material.

In the embodiment shown in FIG. 1, a drying station 60 is locateddownstream of and/or adjacent to the clearcoat station 54 to dry and/orcure the applied clearcoat material and/or optionally one or more of thepreviously applied basecoat compositions. As used herein, “cure” meansthat any crosslinkable components of the material are substantiallycrosslinked as discussed in more detail below. This curing step can becarried out by any conventional drying technique, such as hot airconvection drying using a hot air convection oven (such as an automotiveradiant wall/convection oven which is commercially available from Durr,Haden or Thermal Engineering Corporation) or, if desired, infraredheating, such that any crosslinkable components of the liquid clearcoatmaterial are crosslinked to such a degree that the automobile industryaccepts the coating method as sufficiently complete to transport thecoated automobile body without damage to the clearcoat. Generally, theliquid clearcoat material is heated to a temperature of 120° C. to 150°C. for a period of 20 to 40 minutes to cure the liquid clearcoat.

Alternatively, if one or more of the basecoat compositions were notcured prior to applying the liquid clearcoat material, both the basecoatcompositions and the liquid clearcoat material can be cured together byapplying hot air convection and/or infrared heating using conventionalapparatus to cure both the basecoat compositions and the liquidclearcoat material.

FIG. 2 illustrates an alternative basecoat zone 20 a that can beutilized in the practice of the invention. As shown by dashed lines, inthis embodiment the cut-in station 22 can be optionally located betweenthe first and second basecoat stations 30, 40 (i.e., downstream of thefirst basecoat station 30). Alternatively, the cut-in station 22 can belocated downstream of the second basecoat station 40. Optional dryingdevices (not shown) can also be optionally located downstream of one ormore of the first basecoat station 30, the cut-in station 22, and/or thesecond basecoat station 40, if desired.

Having described exemplary coating systems of the invention, exemplarycoating processes of the invention will now be described.

As described above, in one embodiment, the present invention is directedto a process for forming a multilayer composite coating on a substrate.The process comprises: forming an electrodeposition coating layer on thesubstrate by electrodeposition of a curable electrodepositable coatingcomposition over at least a portion of the substrate; optionally,heating the coated substrate to a temperature and for a time sufficientto cure the electrodeposition coating layer; forming a basecoating layerover the electrodeposition coating layer by depositing an aqueouscurable basecoating composition directly onto at least a portion of theelectrodeposition coating layer; optionally, dehydrating the basecoatinglayer; forming a top coating layer over the basecoating layer bydepositing a curable top coating composition which is substantiallypigment-free directly onto at least a portion of the basecoating layer;and curing the top coating layer, the basecoating layer, and,optionally, the electrodeposition coating layer simultaneously.

The electrodeposition coating composition can be applied to either baremetal or pretreated metal substrates. By “bare metal” is meant a virginmetal substrate that has not been treated with a pretreatmentcomposition such as conventional phosphating solutions, heavy metalrinses and the like. Additionally, for purposes of the presentinvention, ‘bare metal’ substrates can include a cut edge of a substratethat is otherwise treated and/or coated over the non-edge surfaces ofthe substrate.

Before any treatment or application of any coating composition, thesubstrate optionally may be formed into an object of manufacture. Acombination of more than one metal substrate can be assembled togetherto form such an object of manufacture.

The “substrate” upon which the electrodeposition coating composition isdeposited can comprise any electroconductive substrates including thosedescribed in detail below, to which one or more pretreatment and/orprimer coatings have been previously applied. For example, the“substrate” can comprise a metallic substrate and a weldable primercoating over at least a portion of the substrate surface. Theelectrodepositable coating composition described above is thenelectrodeposited and cured over at least a portion thereof. One or moretop coating compositions as described in detail below are subsequentlyapplied over at least a portion of the cured electrodeposited coating.

For example, the substrate can comprise any of the foregoingelectroconductive substrates and a pre-treatment composition appliedover at least a portion of the substrate, the pretreatment compositioncomprising a solution that contains one or more Group IIIB or IVBelement-containing compounds, or mixtures thereof, solubilized ordispersed in a carrier medium, typically an aqueous medium. The GroupIIIB and IVB elements are defined by the CAS Periodic Table of theElements as shown, for example, in the Handbook of Chemistry andPhysics, (60th Ed. 1980). Transition metal compounds and rare earthmetal compounds typically are compounds of zirconium, titanium, hafnium,yttrium and cerium and mixtures thereof. Typical zirconium compounds maybe selected from hexafluorozirconic acid, alkali metal and ammoniumsalts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconiumcarboxylates and zirconium hydroxy carboxylates such ashydrofluorozirconic acid, zirconium acetate, zirconium oxalate, ammoniumzirconium glycolate, ammonium zirconium lactate, ammonium zirconiumcitrate, and mixtures thereof.

The pretreatment composition carrier also can contain a film-formingresin, for example, the reaction products of one or more alkanolaminesand an epoxy-functional material containing at least two epoxy groups,such as those disclosed in U.S. Pat. No. 5,653,823. Other suitableresins include water soluble and water dispersible polyacrylic acidssuch as those as disclosed in U.S. Pat. Nos. 3,912,548 and 5,328,525;phenol-formaldehyde resins as described in U.S. Pat. No. 5,662,746,incorporated herein by reference; water soluble polyamides such as thosedisclosed in WO 95/33869; copolymers of maleic or acrylic acid withallyl ether as described in Canadian patent application 2,087,352; andwater soluble and dispersible resins including epoxy resins,aminoplasts, phenol-formaldehyde resins, tannins, and polyvinyl phenolsas discussed in U.S. Pat. No. 5,449,415.

Further, non-ferrous or ferrous metallic substrates can be pretreatedwith a non-insulating layer of organophosphates or organophosphonatessuch as those described in U.S. Pat. Nos. 5,294,265 and 5,306,526. Suchorganophosphate or organophosphonate pretreatments are availablecommercially from PPG Industries, Inc. under the trade name NUPAL®,Application to the substrate of a non-conductive coating, such asNUPAL®, typically is followed by the step of rinsing the substrate withdeionized water prior to the coalescing of the coating. This ensuresthat the layer of the non-conductive coating is sufficiently thin to benon-insulating, i.e., sufficiently thin such that the non-conductivecoating does not interfere with electroconductivity of the substrate,allowing subsequent electrodeposition of a electrodepositable coatingcomposition. The pretreatment coating composition can further comprisesurfactants that function as aids to improve wetting of the substrate.Generally, the surfactant materials are present in an amount of lessthan about 2 weight percent on a basis of total weight of thepretreatment coating composition. Other optional materials in thecarrier medium include defoamers and substrate wetting agents.

Due to environmental concerns, the pretreatment coating composition canbe free of chromium-containing materials, i.e., the composition containsless than about 2 weight percent of chromium-containing materials(expressed as CrO₃), typically less than about 0.05 weight percent ofchromium-containing materials.

In the pre-treatment process, before depositing the pre-treatmentcomposition upon the surface of the metal substrate, it is usualpractice to remove foreign matter from the metal surface by thoroughlycleaning and degreasing the surface. The surface of the metal substratecan be cleaned by physical or chemical means, such as by mechanicallyabrading the surface or cleaning/degreasing with commercially availablealkaline or acidic cleaning agents which are well know to those skilledin the art, such as sodium metasilicate and sodium hydroxide. Anon-limiting example of a suitable cleaning agent is CHEMKLEEN® 163, analkaline-based cleaner commercially available from PPG Pretreatment andSpecialty Products of Troy, Mich. Acidic cleaners also can be used.Following the cleaning step, the metal substrate is usually rinsed withwater in order to remove any residue. The metal substrate can beair-dried using an air knife, by flashing off the water by briefexposure of the substrate to a high temperature or by passing thesubstrate between squeegee rolls. The pretreatment coating compositioncan be deposited upon at least a portion of the outer surface of themetal substrate. Preferably, the entire outer surface of the metalsubstrate is treated with the pretreatment composition. The thickness ofthe pretreatment film can vary, but is generally less than about 1micrometer, preferably ranges from about 1 to about 500 nanometers, andmore preferably ranges from about 10 to about 300 nanometers.

The pretreatment coating composition is applied to the surface of thesubstrate by any conventional application technique, such as byspraying, immersion or roll coating in a batch or continuous process.The temperature of the pretreatment coating composition at applicationis typically about 10° C. to about 85° C., and preferably about 15° C.to about 60° C. The pH of the pretreatment coating composition atapplication generally ranges from 2.0 to 5.5, and typically from 3.5 to5.5. The pH of the medium may be adjusted using mineral acids such ashydrofluoric acid, fluoroboric acid, phosphoric acid, and the like,including mixtures thereof; organic acids such as lactic acid, aceticacid, citric acid, sulfamic acid, or mixtures thereof; and water solubleor water dispersible bases such as sodium hydroxide, ammonium hydroxide,ammonia, or amines such as triethylamine, methylethyl amine, or mixturesthereof.

Continuous processes typically are used in the coil coating industry andalso for mill application. The pretreatment coating composition can beapplied by any of these conventional processes. For example, in the coilindustry, the substrate typically is cleaned and rinsed and thencontacted with the pretreatment coating composition by roll coating witha chemical coater. The treated strip is then dried by heating, paintedand baked by conventional coil coating processes.

Mill application of the pretreatment composition can be by immersion,spray or roll coating applied to the freshly manufactured metal strip.Excess pretreatment composition is typically removed by wringer rolls.After the pretreatment composition has been applied to the metalsurface, the metal can be rinsed with deionized water and dried at roomtemperature or at elevated temperatures to remove excess moisture fromthe treated substrate surface and cure any curable coating components toform the pretreatment coating. Alternatively, the treated substrate canbe heated to a temperature ranging from 65° C. to 125° C. for 2 to 30seconds to produce a coated substrate having a dried residue of thepretreatment coating composition thereon. If the substrate is alreadyheated from the hot melt production process, no post application heatingof the treated substrate is required to facilitate drying. Thetemperature and time for drying the coating will depend upon suchvariables as the percentage of solids in the coating, components of thecoating composition and type of substrate.

The film coverage of the residue of the pretreatment compositiongenerally ranges from 1 to 10,000 milligrams per square meter(mg/m.sup.2), and usually from 10 to 400 mg/m².

A layer of a weldable primer also can be applied over the substrate,whether or not the substrate has been pretreated. Non-limiting examplesof suitable weldable primers include those described in U.S. Pat. Nos.5,580,371; 5,652,024; 5,584,946; and 3,792,850. The weldable primer cancomprise a reactive functional group-containing film-forming polymer,for example a polyepoxide polymer or an acrylic polymer having epoxyfunctional groups; and a crosslinking agent adapted to react with thefunctional groups of the film-forming polymer. The weldable primercomposition further comprises one or more conductive pigments such ascarbon black, present in an amount sufficient to render the cured primerweldable. A typical weldable primer is BONAZINC®, a zinc-rich millapplied organic film-forming composition, which is commerciallyavailable from PPG Industries, Inc., Pittsburgh, Pa. BONAZINC can beapplied to a thickness of at least 1 micrometer and typically to athickness of 3 to 4 micrometers. Other weldable primers, such as ironphosphide-rich primers, are commercially available.

The optional electrodeposition step of any of the processes of thepresent invention can include immersing the electroconductive substrateinto an electrodeposition bath of an aqueous electrodepositablecomposition, the substrate serving as a cathode in an electrical circuitcomprising the cathode and an anode. Sufficient electrical current isapplied between the electrodes to deposit a substantially continuous,adherent film of the electrodepositable coating composition onto or overat least a portion of the surface of the electroconductive substrate.Also, it should be understood that as used herein, an electrodepositablecomposition or coating formed “over” at least a portion of a “substrate”refers to a composition formed directly on at least a portion of thesubstrate surface, as well as a composition or coating formed over anycoating or pretreatment material which was previously applied to atleast a portion of the substrate. Electrodeposition is usually carriedout at a constant voltage in the range of from 1 volt to severalthousand volts, typically between 50 and 500 volts. Current density isusually between 1.0 ampere and 15 amperes per square foot (10.8 to 161.5amperes per square meter) and tends to decrease quickly during theelectrodeposition process, indicating formation of a continuous,self-insulating film.

Once the electrodepositable coating composition (described in detailbelow) is applied as described above, thereby forming anelectrodeposition coating layer over the substrate, theelectrodeposition coating layer, optionally, is heated to a temperatureand for a time sufficient to cure the electrodeposition coating layer.The coated substrate can be heated to a temperature ranging from 250° to450° F. (121.1° to 232.2° C.), often from 250° to 400° F. (121.1° to204.4° C.), and typically from 300° to 360° (148.9° to 180° C.). Thecuring time can be dependent upon the curing temperature as well asother variables, for example, film thickness of the electrodepositedcoating, level and type of catalyst present in the composition and thelike. For purposes of the present invention, all that is necessary isthat the time be sufficient to effect cure of the electrodepositedcoating on the substrate. For example, the curing time can range from 10minutes to 60 minutes, and typically from 10 to 30 minutes. Thethickness of the resultant cured electrodeposited coating usually rangesfrom 15 to 50 microns.

As used herein, the term “cure” as used in connection with acomposition, e.g., “a cured composition,” shall mean that anycrosslinkable components of the composition are at least partiallycrosslinked. In certain embodiments of the present invention, thecrosslink density of the crosslinkable components, i.e., the degree ofcrosslinking, ranges from 5% to 100% of complete crosslinking. In otherembodiments, the crosslink density ranges from 35% to 85% of fullcrosslinking. In other embodiments, the crosslink density ranges from50% to 85% of full crosslinking. One skilled in the art will understandthat the presence and degree of crosslinking, i.e., the crosslinkdensity, can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA) using a TA Instruments DMA 2980 DMTAanalyzer conducted under nitrogen. This method determines the glasstransition temperature and crosslink density of free films of coatingsor polymers. These physical properties of a cured material are relatedto the structure of the crosslinked network.

The electrodepositable coating composition employed in the processes ofthe present invention can be any of the anionic or cationicelectrodepositable coating compositions well known in the art. Asaforementioned, electrodepostable cationic compositions are typicallyused in the electrocoating of metallic motor vehicle or automotivesubstrates.

Electrodepositable coating compositions usually comprise a resinousphase dispersed in an aqueous medium, the resinous phase comprising (a)an ungelled, active hydrogen group-containing ionic resin, and (b) acuring agent having functional groups reactive with the active hydrogengroups of (a). Such electrodepostable coating compositions typically arein the form of an electrodeposition bath.

By “ungelled” is meant the resins are substantially free of crosslinkingand have an intrinsic viscosity when dissolved in a suitable solvent, asdetermined, for example, in accordance with ASTM-D1795 or ASTM-D4243.The intrinsic viscosity of the reaction product is an indication of itsmolecular weight. A gelled reaction product, on the other hand, since itis of essentially infinitely high molecular weight, will have anintrinsic viscosity too high to measure. As used herein, a reactionproduct that is “substantially free of crosslinking” refers to areaction product that has a weight average molecular weight (Mw), asdetermined by gel permeation chromatography, of less than 1,000,000.

The term “active hydrogen” refers to those groups which are reactivewith isocyanates as determined by the Zerewitnoff test as is describedin the JOURNAL OF THE AMERICAN CHEMICAL SOClETY, Vol. 49, page 3181(1927). For example, the active hydrogens can be derived from hydroxylgroups, primary amine groups and/or secondary amine groups.

Examples of film-forming resins suitable for use in anionicelectrodeposition bath compositions are base-solubilized, carboxylicacid containing polymers such as the reaction product or adduct of adrying oil or semi-drying fatty acid ester with a dicarboxylic acid oranhydride; and the reaction product of a fatty acid ester, unsaturatedacid or anhydride and any additional unsaturated modifying materialswhich are further reacted with polyol. Also suitable are the at leastpartially neutralized interpolymers of hydroxy-alkyl esters ofunsaturated carboxylic acids, unsaturated carboxylic acid and at leastone other ethylenically unsaturated monomer. Still another suitableelectrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., avehicle containing an alkyd resin and an amine-aldehyde resin. Yetanother anionic electrodepositable resin composition comprises mixedesters of a resinous polyol. These compositions are described in detailin U.S. Pat. No. 3,749,657 at col. 9, lines 1 to 75 and col. 10, lines 1to 13, all of which are herein incorporated by reference. Other acidfunctional polymers can also be used such as phosphatized polyepoxide orphosphatized acrylic polymers as are well known to those skilled in theart.

Cationic polymers suitable for use in the electrodepositable coatingcompositions can include any of a number of cationic polymers well knownin the art so long as the polymers are “water dispersible,” i.e.,adapted to be solubilized, dispersed or emulsified in water. Suchpolymers comprise cationic functional groups to impart a positivecharge.

Suitable examples of cationic film-forming resins include amine saltgroup-containing resins such as the acid-solubilized reaction productsof polyepoxides and primary or secondary amines such as those describedin U.S. Pat. Nos. 3,663,389; 3,984,299; 3,947,338; and 3,947,339.Usually, these amine salt group-containing resins are used incombination with a blocked isocyanate curing agent. The isocyanate canbe fully blocked as described in the aforementioned U.S. Pat. No.3,984,299 or the isocyanate can be partially blocked and reacted withthe resin backbone such as described in U.S. Pat. No. 3,947,338. Also,one-component compositions as described in U.S. Pat. No. 4,134,866 andDE-OS No. 2,707,405 can be used as the film-forming resin. Besides theepoxy-amine reaction products, film-forming resins can also be selectedfrom cationic acrylic resins such as those described in U.S. Pat. Nos.3,455,806 and 3,928,157.

Besides amine salt group-containing resins, quaternary ammonium saltgroup-containing resins can also be employed. Examples of these resinsare those which are formed from reacting an organic polyepoxide with atertiary amine salt. Such resins are described in U.S. Pat. Nos.3,962,165; 3,975,346; and 4,001,101. Examples of other cationic resinsare ternary sulfonium salt group-containing resins and quaternaryphosphonium salt-group containing resins such as those described in U.S.Pat. Nos. 3,793,278 and 3,984,922, respectively. Also, film-formingresins which cure via transesterification such as described in EuropeanApplication No. 12463 can be used. Further, cationic compositionsprepared from Mannich bases such as described in U.S. Pat. No. 4,134,932can be used.

Most often, the resin (a) is a positively charged resin which containsprimary and/or secondary amine groups. Such resins are described in U.S.Pat. Nos. 3,663,389; 3,947,339 and 4,116,900. In U.S. Pat. No.3,947,339, a polyketimine derivative of a polyamine such asdiethylenetriamine or triethylenetetraamine is reacted with apolyepoxide. When the reaction product is neutralized with acid anddispersed in water, free primary amine groups are generated. Also,equivalent products are formed when polyepoxide is reacted with excesspolyamines such as diethylenetriamine and triethylenetetraamine and theexcess polyamine vacuum stripped from the reaction mixture. Suchproducts are described in U.S. Pat. Nos. 3,663,389 and 4,116,900.

The active hydrogen-containing, ionic electrodepositable resin describedabove can be present in the electrodeposition baths used in theprocesses of the present invention in amounts ranging from 1 to 60percent by weight, often from 5 to 25 based on total weight of theelectrodeposition bath.

The resinous phase of the electrodeposition baths suitable for use inthe processes of the present invention further comprises (b) a curingagent adapted to react with the active hydrogen groups of the ionicelectrodepositable resin (a) described immediately above. Both blockedorganic polyisocyanate and aminoplast curing agents are suitable for usein the present invention, although blocked isocyanates typically areused for cathodic electrodeposition.

Aminoplast resins, typically used as the curing agent for anionicelectrodeposition, are the condensation products of amines or amideswith aldehydes. Examples of suitable amine or amides are melamine,benzoguanamine, urea and similar compounds. Generally, the aldehydeemployed is formaldehyde, although products can be made from otheraldehydes such as acetaldehyde and furfural. The condensation productscontain methylol groups or similar alkylol groups depending on theparticular aldehyde employed. Preferably, these methylol groups areetherified by reaction with an alcohol. Various alcohols employedinclude monohydric alcohols containing from 1 to 4 carbon atoms such asmethanol, ethanol, isopropanol, and n-butanol, with methanol beingpreferred. Aminoplast resins are commercially available from Cytec underthe trademark CYMEL and from Solutia under the trademark RESIMENE.

The aminoplast curing agents typically are utilized in conjunction withthe active hydrogen containing anionic electrodepositable resin inamounts ranging from about 5 percent to about 60 percent by weight,preferably from about 20 percent to about 40 percent by weight, thepercentages based on the total weight of the resin solids in theelectrodeposition bath.

Typically, curing agents for use in cathodic electrodeposition includeblocked organic polyisocyanates. The polyisocyanates can be fullyblocked as described in U.S. Pat. No. 3,984,299 column 1 lines 1 to 68,column 2 and column 3 lines 1 to 15, or partially blocked and reactedwith the polymer backbone as described in U.S. Pat. No. 3,947,338 column2 lines 65 to 68, column 3 and column 4 lines 1 to 30, which areincorporated by reference herein. By “blocked” is meant that theisocyanate groups have been reacted with a compound so that theresultant blocked isocyanate group is stable to active hydrogens atambient temperature but reactive with active hydrogens in the filmforming polymer at elevated temperatures usually between 90° C. and 200°C.

Suitable polyisocyanates include aromatic and aliphatic polyisocyanates,including cycloaliphatic polyisocyanates and representative examplesinclude diphenylmethane-4,4′-diisocyanate (MDI), 2,4- or 2,6-toluenediisocyanate (TDI), including mixtures thereof, p-phenylenediisocyanate, tetramethylene and hexamethylene diisocyanates,dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, mixturesof phenylmethane-4,4′-diisocyanate and polymethylenepolyphenylisocyanate. Higher polyisocyanates such as triisocyanates canbe used, for example, triphenyl methane-4,4′,4″-triisocyanate.Isocyanate prepolymers prepared in conjunction with polyols such asneopentyl glycol and trimethylolpropane and with polymeric polyols suchas polycaprolactone diols and triols (NCO/OH equivalent ratio greaterthan 1) can also be used.

The polyisocyanate curing agents typically can be utilized inconjunction with the active hydrogen containing cationicelectrodepositable resin in amounts ranging from 5 percent to 60 percentby weight, and typically from 20 percent to 50 percent by weight, thepercentages based on the total weight of the resin solids of theelectrodeposition bath.

The aqueous electrodepositable coating compositions are in the form ofan aqueous dispersion. The term “dispersion” is believed to be atwo-phase transparent, translucent or opaque resinous system in whichthe resin is in the dispersed phase and the water is in the continuousphase. The average particle size of the resinous phase is generally lessthan 1.0 and usually less than 0.5 microns, preferably less than 0.15micron.

The concentration of the resinous phase in the aqueous medium is atleast 1 and usually from 2 to 60 percent by weight based on total weightof the aqueous dispersion. When the compositions of the presentinvention are in the form of resin concentrates, they generally have aresin solids content ranging from 20 to 60 percent by weight based onweight of the aqueous dispersion.

In one particular embodiment of the present invention, theelectrodepositable coating composition is a photodegradation-resistantcomposition comprising a resinous phase comprising: (1) one or moreungelled, active hydrogen-containing, cationic amine saltgroup-containing resins which are electrodepositable on a cathode, and(2) one or more at least partially blocked aliphatic polyisocyanatecuring agents. The amine salt groups of the cationic resin (1) arederived from pendant and/or terminal amine groups having the followingstructures (I) or (II):

wherein R represents H or C₁ to C₁₈ alkyl; R₁, R₂, R₃, and R₄ are thesame or different, and each independently represents H or C₁ to C₄alkyl; and X and Y can be the same or different, and each independentlyrepresents a hydroxyl group or an amino group.

By “terminal and/or pendant” is meant that primary and/or secondaryamino groups are present as a substituent which is pendant from or inthe terminal position of the polymeric backbone, or, alternatively, isan end-group substituent of a group which is pendant and/or terminalfrom the polymer backbone. In other words, the amino groups from whichthe cationic amine salt groups are derived are not within the polymericbackbone.

By “alkyl” is meant alkyl and aralkyl, cyclic or acyclic, linear orbranched monovalent hydrocarbon groups. The alkyl groups can beunsubstituted or substituted with one or more heteroaoms, for example,non-carbon, non-hydrogen atoms such as one or more oxygen, nitrogen orsulfur atoms.

The pendant and/or terminal amino groups represented by structures (I)and (II) above can be derived from a compound selected from the groupconsisting of ammonia, methylamine, diethanolamine, diisopropanolamine,N-hydroxyethyl ethylenediamine, diethylenetriamine, and mixturesthereof. One or more of these compounds is reacted with one or more ofthe above described polymers, for example, a polyepoxide polymer, wherethe epoxy groups are ring-opened via reaction with a polyamine, therebyproviding terminal amino groups and secondary hydroxyl groups, or anacrylic polymer having epoxy functional groups derived fromepoxy-functional, ethylenically unsaturated monomers, such as glycidylmethacrylate.

In one particular embodiment of the invention, the cationic saltgroup-containing polymer contains amine salt groups which are derivedfrom one or more pendant and/or terminal amino groups having thestructure (II) above, such that when the electrodepositable coatingcomposition is electrodeposited and cured, at least twoelectron-withdrawing groups (as described in detail below) are bonded inthe beta-position relative to substantially all of the nitrogen atomspresent in the cured electrodeposited coating. In a further embodimentof the invention, when the electrodepositable coating composition iselectrodeposited and cured, three electron-withdrawing groups are bondedin the beta-position relative to substantially all of the nitrogen atomspresent in the cured electrodeposited coating. By “substantially all” ofthe nitrogen atoms present in the cured electrodeposited coating ismeant at least 65 percent, and typically 90 percent, of all nitrogenatoms present in the cured electrodeposited coating which are derivedfrom the amine used to form the cationic amine salt groups.

As discussed below, the electron-withdrawing groups to which referenceis made herein are formed by the reaction of a polyisocyanate curingagent with the pendant and/or terminal hydroxyl and/or amino groupsrepresented by X and Y in structure (II) which are bonded in thebeta-position relative to the nitrogen atom depicted in this structure.The amount of free or unbound amine nitrogen present in a cured freefilm of the electrodepositable composition can be determined as follows.The cured free coating film can be cryogenically milled and dissolvedwith acetic acid then titrated potentiometrically with acetousperchloric acid to determine the total base content of the sample. Theprimary amine content of the sample can be determined by reaction of theprimary amine with salicylaldehyde to form an untitratable azomethine.Any unreacted secondary and tertiary amine then can be determined bypotentiometric titration with perchloric acid. The difference betweenthe total basicity and this titration represents the primary amine. Thetertiary amine content of the sample can be determined by potentiometrictitration with perchloric acid after reaction of the primary andsecondary amine with acetic anhydride to form the corresponding amides.

In one embodiment of the present invention, the terminal amino groupshave the structure (II) where both X and Y comprise primary aminogroups, e.g., the amino group is derived from diethylenetriamine. Itshould be understood that in this instance, prior to reaction with thepolymer, the primary amino groups can be blocked, for example, byreaction with a ketone such as methyl ethyl ketone, to form thediketimine. Such ketimines are those described in U.S. Pat. No.4,104,147, column 6, line 23 to column 7, line 23. The ketimine groupscan decompose upon dispersing the amine-epoxy reaction product in water,thereby providing free primary amine groups as curing reaction sites.

Minor amounts (e.g., an amount which would represent less than or equalto 5 percent of total amine nitrogen present in the composition) ofamines such as mono, di, and trialkylamines and mixed aryl-alkyl amineswhich do not contain hydroxyl groups, or amines substituted with groupsother than hydroxyl provided that the inclusion of such amines does notnegatively affect the photodegradation resistance of the curedelectrodeposited coating. Specific examples include monoethanolamine,N-methylethanolamine, ethylamine, methylethylamine, triethylamine,N-benzyldimethylamine, dicocoamine and N,N-dimethylcyclohexylamine.

The reaction of the above-described amines with epoxide groups on thepolymer takes place upon mixing of the amine and polymer. The amine maybe added to the polymer or vice versa. The reaction can be conductedneat or in the presence of a suitable solvent such as methyl isobutylketone, xylene, or 1-methoxy-2-propanol. The reaction is generallyexothermic and cooling may be desired. However, heating to a moderatetemperature of about 50° C. to 150° C. may be done to hasten thereaction.

The active hydrogen-containing, cationic salt group-containing polymerused in the electrodepositable composition is prepared from componentsselected so as to maximize the photodegradation resistance of thepolymer and the resulting cure electrodeposited composition. Though notintending to be bound by any theory, it is believed thatphotodegradation resistance (i.e., resistance to visible and ultravioletlight degradation) of the cured electrodeposited coating can becorrelated with the location and nature of nitrogen-containing cationicgroups used for dispersion of the active hydrogen-containing, cationicamine salt group-containing resin.

For purposes of the present invention, the amines from which the pendantand/or terminal amino groups are derived comprise primary and/orsecondary amine groups such that the active hydrogens of said amineswill be consumed by reaction with the at least partially blockedaliphatic polyisocyanate curing agent to form urea groups or linkagesduring the curing reaction. The urea groups formed during the curingreaction appear to have no significant negative influence onphotodegradation resistance of the cured electrodeposited coating.

In one embodiment of the present invention, a polyepoxide polymer can be“defunctionalized” with an excess of ammonia, yielding a polymercomprising one or more of the following structural units (III). Cationicsalt groups subsequently can be formed by admixing such a polymer with asuitable solubilizing acid to promote dispersion in water.

In an alternative embodiment of the present invention, the cationicpolymer (1) can comprise a polyepoxide polymer having pendant and/orterminal amino groups comprising primary amine groups from whichcationic amine salts can be formed. Such a polymer can be prepared, forexample, by reacting diethylene triamine bis-ketamine with an epoxygroup containing polymer, followed by hydrolysis to decompose theketimine. Such a polymer can comprise one or more of the followingstructural units (IV):

It was surprising to find that, despite the presence of the tertiarynitrogen in this structural unit, electrodeposited compositionscomprising such polymers exhibit improved photodegradation resistance.Without intending to be bound by theory, it is believed that this is dueto the formation during the cure reaction with the polyisocyanate curingagent of two strong electron-withdrawing groups (in this case, ureagroups) bonded in the beta-position relative to the tertiary nitrogen.

Likewise, it was found that polymers comprising other structural unitshaving isocyanate-reactive groups in the beta-position relative to thenitrogen atom also can exhibit similar photodegradation resistance. Suchpolymers can comprise, for example, the following structural units (V)and (VI):

Upon reaction of polymers having one or more of the structural units(VI) with the polyisocyanate curing agent, electron-withdrawing urethanegroups are formed at the beta-position relative to the tertiary nitrogenatoms which are derived from the pendant and/or terminal amino groups.Likewise, upon reaction of polymers having one or more of the structuralunits (V) with the polyisocyanate curing agent, electron-withdrawingurethane and urea groups are formed at the beta-position relative to thetertiary nitrogen atoms derived from the pendant and/or terminal aminogroups.

As used herein, by “electron-withdrawing group” is meant a group (e.g.,a urethane or urea group) that tends to draw electrons orelectronegative charge from the amine nitrogen atom, thereby renderingthe amine nitrogen less basic. Such electron-withdrawing groups can bederived from the reaction of the polyisocyanate curing agent with thehydroxyl and/or amino groups, represented by X and Y in structure (II)above, which are pendant and/or terminal from the resin. Moreover, itshould be understood that for purposes of the present invention, theurethane groups derived from the reaction of the polyisocyanate curingagent and the hydroxyl groups along the polymer backbone, and/or thesecondary hydroxyl groups which are formed upon the ring opening of anepoxy group, are not intended to be within the meaning of the term“electron-withdrawing group(s)”.

It has been found that polymers comprising primarily structural unitssuch as structural units (VII) and/or (VIII) below, where R representsan unsubstituted alkyl group, exhibit significantly poorerphotodegradation resistance as compared to those polymers discussedimmediately above. Without intending to be bound by theory, it isbelieved that the poorer photodegradation resistance of such polymerscomprising primarily structural units (VII) and/or (VIII) can beattributed to the fact that the basic nitrogens are present in thebackbone of the polymer (and are not pendant and/or terminal withrespect to the polymer backbone) and/or do not react with thepolyisocyanate curing agent to generate two electron-withdrawing groupsin the beta-position relative to the basic amine group.

It can be inferred by those skilled in the art from the generally poorercure response of cationic epoxies containing a preponderance ofstructural units (VII) and (VIII), that the hydroxyl groups beta tophenoxy groups on the backbone of (VII) and near the end of structuralunit (VIII) do not effectively participate in cure, i.e. they are notcompletely converted to electron-withdrawing urethane groups during thecuring step. Also, it should here be noted that the degree ofconsumption of basic nitrogen by reaction with the polyisocyanate curingagent can be measured by titration of the cryogenically groundelectrodepositable composition after the curing step as described above.

If desired, a minor amount of the polymer(s) having the structural units(VII) and/or (VIII) can be included in the electrodepositable coatingcompositions of the present invention, provided that such polymers arenot present in an amount sufficient to negatively affectphotodegradation resistance of the cured electrodeposited coating.

The active hydrogen-containing, terminal amino group-containing polymeris rendered cationic and water dispersible by at least partialneutralization with an acid. Suitable acids include organic andinorganic acids such as formic acid, acetic acid, lactic acid,phosphoric acid, dimethylolpropionic acid, and sulfamic acid. Mixturesof acids can be used. The extent of neutralization varies with theparticular reaction product involved. However, sufficient acid should beused to disperse the electrodepositable composition in water. Typically,the amount of acid used provides at least 30 percent of the totaltheoretical neutralization. Excess acid may also be used beyond theamount required for 100 percent total theoretical neutralization.

The extent of cationic salt group formation should be such that when thepolymer is mixed with an aqueous medium and the other ingredients, astable dispersion of the electrodepositable composition will form. By“stable dispersion” is meant one that does not settle or is easilyredispersible if some settling occurs. Moreover, the dispersion shouldbe of sufficient cationic character that the dispersed particles willmigrate toward and electrodeposit on a cathode when an electricalpotential is set up between an anode and a cathode immersed in theaqueous dispersion.

Generally, the cationic polymer is ungelled and contains from about 0.1to 3.0, preferably from about 0.1 to 0.7 millequivalents of cationicsalt group per gram of polymer solids.

The active hydrogens associated with the cationic polymer include anyactive hydrogens which are reactive with isocyanates within thetemperature range of about 93° C. to 204.degree. C., preferably about121° C. to 177° C. Typically, the active hydrogens are selected from thegroup consisting of hydroxyl and primary and secondary amino, includingmixed groups such as hydroxyl and primary amino. Preferably, the polymerwill have an active hydrogen content of about 1.7 to 10 millequivalents,more preferably about 2.0 to 5 millequivalents of active hydrogen pergram of polymer solids.

The cationic salt group-containing polymer can be present in thephotodegradation-resistant electrodepositable composition used in theprocesses of the present invention in an amount ranging from 20 to 80percent, often from 30 to 75 percent by weight, and typically from 50 to70 percent by weight based on the total combined weight of resin solidsof the cationic salt group-containing polymer and the curing agent.

As mentioned above, the resinous phase of the photodegradation-resistantelectrodepositable coating composition further comprises a curing agent(2) adapted to react with the active hydrogen groups of the cationicelectrodepositable resin described immediately above. In one embodimentof the present invention, the curing agent comprises one or more atleast partially blocked aliphatic polyisocyanates. In this embodiment, aminor amount (i.e. less than 10, preferably less than 5 weight percentof total resin solids of the curing agent present in the composition) ofaromatic polyisocyanate can be included, provided that the aromaticpolyisocyanate is not present in an amount sufficient to deleteriouslyaffect the photodegradation resistance of the cured electrodepositedcomposition.

The aliphatic polyisocyanates can be fully blocked as described in U.S.Pat. No. 3,984,299 column 1 lines 1 to 68, column 2 and column 3 lines 1to 15, or partially blocked and reacted with the polymer backbone asdescribed in U.S. Pat. No. 3,947,338 column 2 lines 65 to 68, column 3and column 4 lines 1 to 30. In one embodiment of the present invention,the polyisocyanate curing agent is a fully blocked polyisocyanate withsubstantially no free isocyanate groups.

Diisocyanates typically are used, although higher polyisocyanates can beused in lieu of or in combination with diisocyanates. Examples ofaliphatic polyisocyanates suitable for use as curing agents includecycloaliphatic and araliphatic polyisocyanates such as 1,6-hexamethylenediisocyanate, isophorone diisocyanate,bis-(isocyanatocyclohexyl)methane, polymeric 1,6-hexamethylenediisocyanate, trimerized isophorone diisocyanate, norbornanediisocyanate and mixtures thereof. In a particular embodiment of thepresent invention, the curing agent comprises a fully blockedpolyisocyanate selected from a polymeric 1,6-hexamethylene diisocyanate,isophorone diisocyanate, and mixtures thereof. In another embodiment ofthe present invention the polyisocyanate curing agent comprises a fullyblocked trimer of hexamethylene diisocyanate available as DesmodurN3300® from Bayer Corporation.

In one embodiment of the present invention, the aliphatic polyisocyanatecuring agent is at least partially blocked with at least one blockingagent selected from a 1,2-alkane diol, for example 1,2-propanediol, a1,3-alkane diol, for example 1,3-butanediol, a benzylic alcohol, forexample, benzyl alcohol, an allylic alcohol, for example, allyl alcohol,caprolactam, a dialkylamine, for example dibutylamine, and mixturesthereof. In a further embodiment of the present invention, the aliphaticpolyisocyanate curing agent is at least partially blocked with at leastone 1,2-alkane diol having three or more carbon atoms, for example1,2-butanediol.

If desired, the blocking agent can further comprise minor amounts ofother well known blocking agents such as aliphatic, cycloaliphatic, oraromatic alkyl monoalcohol or phenolic compound, including, for example,lower aliphatic alcohols such as methanol, ethanol, and n-butanol;cycloaliphatic alcohols such as cyclohexanol; aromatic-alkyl alcoholssuch as phenyl carbinol and methylphenyl carbinol; and phenoliccompounds such as phenol itself and substituted phenols wherein thesubstituent's do not affect coating operations, such as cresol andnitrophenol. Glycol ethers and glycol amines may also be used asblocking agents. Suitable glycol ethers include ethylene glycol butylether, diethylene glycol butyl ether, ethylene glycol methyl ether andpropylene glycol methyl ether. Other suitable blocking agents includeoximes such as methyl ethyl ketoxime, acetone oxime and cyclohexanoneoxime. As mentioned above, these conventional blocking agents can beused in minor amounts provided that they are not present in amountssufficient to deleteriously affect photodegradation resistance of thecured electrodeposited coating.

The at least partially blocked polyisocyanate curing agent (2) can bepresent in the photodegradation-resistant electrodepositable compositionused in the processes of the present invention in an amount ranging from80 to 20 percent, often from 75 to 30, and typically from 70 to 50percent by weight, based on the total combined weight of resin solids ofthe cationic salt group-containing polymer and the curing agent.

Suitable photodegradation-resistant electrodeposition coatingcompositions are described in U.S. patent application Ser. No.10/005,830, incorporated herein by reference.

Any of the electrodepositable coating compositions suitable for use inthe processes of the present invention, typically further comprise otheroptional ingredients. For example, the resinous binder is dispersed inan aqueous media which comprises primarily water. Besides water, theaqueous medium may contain a coalescing solvent, for example,hydrocarbons, alcohols, esters, ethers and ketones, such as isopropanol,butanol, 2-ethylhexanol, isophorone, 2-methoxypentanone, ethylene andpropylene glycol and the monoethyl, monobutyl and monohexyl ethers ofethylene glycol. A pigment composition, for example, those describedbelow with reference to the basecoating compositions, and, if desired,various additives such as surfactants, wetting agents or catalysts alsocan be included in the dispersion. Other ingredients can includecorrosion inhibitive materials, for example, rare earth metal compound,such as soluble, insoluble, organic and inorganic salts of rare earthmetals such as, inter alia, yttrium, bismuth, zirconium, and tungsten.Also, hindered amine light stabilizers and/or ultraviolet lightabsorbers can be included in the electrodepositable coatingcompositions.

In the processes of the present invention, any of the curableelectrodepositable coating compositions described above can beelectrophoretically deposited onto at least a portion of any of avariety of electroconductive substrates, including various metallicsubstrates. Suitable metallic substrates can include ferrous metals andnon-ferrous metals. Suitable ferrous metals include iron, steel, andalloys thereof. Non-limiting examples of useful steel materials includecold-rolled steel, galvanized (i.e., zinc coated) steel,electrogalvanized steel, stainless steel, pickled steel, GALVANNEAL®,GALVALUMEAND®, GALVAN® zinc-aluminum alloys coated upon steel, andcombinations thereof. Useful non-ferrous metals include conductivecarbon coated materials, aluminum, copper, zinc, magnesium and alloysthereof. Cold rolled steel also is suitable when pretreated with asolution such as a metal phosphate solution, an aqueous solutioncontaining at least one Group IIIB or IVB metal, an organophosphatesolution, an organophosphonate solution and combinations of the above asare discussed below. Combinations or composites of ferrous andnon-ferrous metals can also be used.

In one embodiment, the process of the present invention furthercomprises the step of forming a basecoat over the electrodepositioncoating layer by depositing an aqueous curable basecoating compositiondirectly onto at least a portion of the electrodeposition coating layer.The basecoating composition typically comprise an aqueous basecoatingcomposition such as any of the aqueous basecoating compositions wellknown in the art.

As used herein, by applying a composition “onto” or “directly onto” atleast a portion of a substrate or previously formed coating layer ismeant that the composition is applied onto the substrate or coatinglayer and is in surface contact with the substrate or coating layer,with no intervening coating layer(s).

The aqueous basecoating compositions useful in the processes of thepresent invention typically comprise (i) a resinous binder comprising apolymer, which typically comprises reactive functional groups; and (ii)a pigment composition comprising one or more pigments dispersed in theresinous binder (i). The polymer can serve as a main film-formingpolymer of the basecoating composition, it can serve as a pigment grindvehicle, or both.

The polymer which comprises the first resin binder (or the secondresinous binder as described below) (i) can be selected from any of avariety of polymers known in the art, for example those polymersselected from the group consisting of an acrylic polymer, a polyesterpolymer, a polyurethane polymer, a polyether polymer, a polyepoxidepolymer, a silicon-containing polymer, mixtures thereof, and copolymersthereof, for example, “hybrid” resinous binders such as a polymerprepared by co-polymerizing one or more ethylenically unsaturatedmonomers (such as any of those described below) in the presence of apolyester polymer (as described in detail below). As used herein, by“silicon-containing polymers” is meant a polymer comprising one or more—SiO— units in the backbone. Such silicon-based polymers can includehybrid polymers, such as those comprising organic polymeric blocks withone or more —SiO— units in the backbone. The resinous binder (i) alsousually comprises a curing agent having functional groups reactive withthe functional groups of the film-forming polymer.

The polymer can comprise at least one reactive functional group selectedfrom a hydroxyl group, a carboxyl group, an isocyanate group, a blockedisocyanate group, a primary amine group, a secondary amine group, anamide group, a carbamate group, a urea group, a urethane group, a vinylgroup, an unsaturated ester group, a maleimide group, a fumarate group,an anhydride group, a hydroxy alkylamide group, an epoxy group, andmixtures of such groups. For example, suitable hydroxyl group-containingpolymers can include acrylic polyols, polyester polyols, polyurethanepolyols, polyether polyols, and mixtures thereof.

Suitable hydroxyl group and/or carboxyl group-containing acrylicpolymers can be prepared from polymerizable ethylenically unsaturatedmonomers and are typically copolymers of (meth)acrylic acid and/orhydroxylalkyl esters of (meth)acrylic acid with one or more otherpolymerizable ethylenically unsaturated monomers such as alkyl esters of(meth)acrylic acid including methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate and 2-ethyl hexylacrylate, and vinyl aromaticcompounds such as styrene, alpha-methyl styrene, and vinyl toluene. Asused herein, “(meth)acrylate” and like terms is intended to include bothacrylates and methacrylates.

In a one embodiment of the present invention the acrylic polymer can beprepared from ethylenically unsaturated, beta-hydroxy ester functionalmonomers. Such monomers can be derived from the reaction of anethylenically unsaturated acid functional monomer, such asmonocarboxylic acids, for example, acrylic acid, and an epoxy compoundwhich does not participate in the free radical initiated polymerizationwith the unsaturated acid monomer. Examples of such epoxy compoundsinclude glycidyl ethers and esters. Suitable glycidyl ethers includeglycidyl ethers of alcohols and phenols such as butyl glycidyl ether,octyl glycidyl ether, phenyl glycidyl ether and the like. Suitableglycidyl esters include those which are commercially available fromShell Chemical Company under the tradename CARDURA E; and from ExxonChemical Company under the tradename GLYDEXX-10. Alternatively, thebeta-hydroxy ester functional monomers can be prepared from anethylenically unsaturated, epoxy functional monomer, for exampleglycidyl(meth)acrylate and allyl glycidyl ether, and a saturatedcarboxylic acid, such as a saturated monocarboxylic acid, for exampleisostearic acid.

Epoxy functional groups can be incorporated into the polymer preparedfrom polymerizable ethylenically unsaturated monomers by copolymerizingoxirane group-containing monomers, for example glycidyl(meth)acrylateand allyl glycidyl ether, with other polymerizable ethylenicallyunsaturated monomers, such as those discussed above. Preparation of suchepoxy functional acrylic polymers is described in detail in U.S. Pat.No. 4,001,156 at columns 3 to 6, incorporated herein by reference.

Carbamate functional groups can be incorporated into the polymerprepared from polymerizable ethylenically unsaturated monomers bycopolymerizing, for example, the above-described ethylenicallyunsaturated monomers with a carbamate functional vinyl monomer such as acarbamate functional alkyl ester of methacrylic acid. Useful carbamatefunctional alkyl esters can be prepared by reacting, for example, ahydroxyalkyl carbamate, such as the reaction product of ammonia andethylene carbonate or propylene carbonate, with methacrylic anhydride.Other useful carbamate functional vinyl monomers include, for instance,the reaction product of hydroxyethyl methacrylate, isophoronediisocyanate, and hydroxypropyl carbamate; or the reaction product ofhydroxypropyl methacrylate, isophorone diisocyanate, and methanol. Stillother carbamate functional vinyl monomers may be used, such as thereaction product of isocyanic acid (HNCO) with a hydroxyl functionalacrylic or methacrylic monomer such as hydroxyethyl acrylate, and thosedescribed in U.S. Pat. No. 3,479,328, incorporated herein by reference.Carbamate functional groups can also be incorporated into the acrylicpolymer by reacting a hydroxyl functional acrylic polymer with a lowmolecular weight alkyl carbamate such as methyl carbamate. Pendantcarbamate groups can also be incorporated into the acrylic polymer by a“transcarbamoylation” reaction in which a hydroxyl functional acrylicpolymer is reacted with a low molecular weight carbamate derived from analcohol or a glycol ether. The carbamate groups exchange with thehydroxyl groups yielding the carbamate functional acrylic polymer andthe original alcohol or glycol ether. Also, hydroxyl functional acrylicpolymers can be reacted with isocyanic acid to provide pendent carbamategroups. Likewise, hydroxyl functional acrylic polymers can be reactedwith urea to provide pendent carbamate groups.

The polymers prepared from polymerizable ethylenically unsaturatedmonomers can be prepared by solution polymerization techniques, whichare well-known to those skilled in the art, in the presence of suitablecatalysts such as organic peroxides or azo compounds, for example,benzoyl peroxide or N,N-azobis(isobutylronitrile). The polymerizationcan be carried out in an organic solution in which the monomers aresoluble by techniques conventional in the art. Alternatively, thesepolymers can be prepared by aqueous emulsion or dispersionpolymerization techniques which are well-known in the art. The ratio ofreactants and reaction conditions are selected to result in an acrylicpolymer with the desired pendent functionality.

Polyester polymers are also useful in the coating compositions of theinvention as the film-forming polymer. Useful polyester polymerstypically include the condensation products of polyhydric alcohols andpolycarboxylic acids. Suitable polyhydric alcohols can include ethyleneglycol, neopentyl glycol, trimethylol propane, and pentaerythritol.Suitable polycarboxylic acids can include adipic acid, 1,4-cyclohexyldicarboxylic acid, and hexahydrophthalic acid. Besides thepolycarboxylic acids mentioned above, functional equivalents of theacids such as anhydrides where they exist or lower alkyl esters of theacids such as the methyl esters can be used. Also, small amounts ofmonocarboxylic acids such as stearic acid can be used. The ratio ofreactants and reaction conditions are selected to result in a polyesterpolymer with the desired pendent functionality, i.e., carboxyl orhydroxyl functionality.

For example, hydroxyl group-containing polyesters can be prepared byreacting an anhydride of a dicarboxylic acid such as hexahydrophthalicanhydride with a diol such as neopentyl glycol in a 1:2 molar ratio.Where it is desired to enhance air-drying, suitable drying oil fattyacids may be used and include those derived from linseed oil, soya beanoil, tall oil, dehydrated castor oil, or tung oil.

Carbamate functional polyesters can be prepared by first forming ahydroxyalkyl carbamate that can be reacted with the polyacids andpolyols used in forming the polyester. Alternatively, terminal carbamatefunctional groups can be incorporated into the polyester by reactingisocyanic acid with a hydroxy functional polyester. Also, carbamatefunctionality can be incorporated into the polyester by reacting ahydroxyl polyester with a urea. Additionally, carbamate groups can beincorporated into the polyester by a transcarbamoylation reaction.Preparation of suitable carbamate functional group-containing polyestersare those described in U.S. Pat. No. 5,593,733 at column 2, line 40 tocolumn 4, line 9, incorporated herein by reference.

In one embodiment of the present invention, the first basecoatingcomposition can comprise less than 50 weight percent, may comprise lessthan 40 weight percent, and may comprise less than 30 weight percent ofa hybrid resin prepared by co-polymerizing one or more polymerizableethylenically unsaturated monomers, such as any of those previouslydiscussed with respect to the acrylic polymers, in the presence of oneor more polyester polymers, such as any of those described immediatelyabove.

Polyurethane polymers containing terminal isocyanate or hydroxyl groupsalso can be used as the polymer (d) in the coating compositions of theinvention. The polyurethane polyols or NCO-terminated polyurethaneswhich can be used are those prepared by reacting polyols includingpolymeric polyols with polyisocyanates. Polyureas containing terminalisocyanate or primary and/or secondary amine groups which also can beused are those prepared by reacting polyamines including polymericpolyamines with polyisocyanates. The hydroxyl/isocyanate oramine/isocyanate equivalent ratio is adjusted and reaction conditionsare selected to obtain the desired terminal groups. Examples of suitablepolyisocyanates include those described in U.S. Pat. No. 4,046,729 atcolumn 5, line 26 to column 6, line 28, incorporated herein byreference. Examples of suitable polyols include those described in U.S.Pat. No. 4,046,729 at column 7, line 52 to column 10, line 35,incorporated herein by reference. Examples of suitable polyaminesinclude those described in U.S. Pat. No. 4,046,729 at column 6, line 61to column 7, line 32 and in U.S. Pat. No. 3,799,854 at column 3, lines13 to 50, both incorporated herein by reference.

Carbamate functional groups can be introduced into the polyurethanepolymers by reacting a polyisocyanate with a polyester having hydroxylfunctionality and containing pendent carbamate groups. Alternatively,the polyurethane can be prepared by reacting a polyisocyanate with apolyester polyol and a hydroxyalkyl carbamate or isocyanic acid asseparate reactants. Examples of suitable polyisocyanates are aromaticisocyanates, such as 4,4′-diphenylmethane diisocyanate, 1,3-phenylenediisocyanate and toluene diisocyanate, and aliphatic polyisocyanates,such as 1,4-tetramethylene diisocyanate and 1,6-hexamethylenediisocyanate. Cycloaliphatic diisocyanates, such as 1,4-cyclohexyldiisocyanate and isophorone diisocyanate also can be employed.

Examples of suitable polyether polyols include polyalkylene etherpolyols such as those having the following structural formulas (IX) or(X):

wherein the substituent R is hydrogen or a lower alkyl group containingfrom 1 to 5 carbon atoms including mixed substituent's, and n has avalue typically ranging from 2 to 6 and m has a value ranging from 8 to100 or higher. Exemplary polyalkylene ether polyols includepoly(oxytetramethylene)glycols, poly(oxytetraethylene)glycols,poly(oxy-1,2-propylene)glycols, and poly(oxy-1,2-butylene)glycols.

Also useful are polyether polyols formed from oxyalkylation of variouspolyols, for example, glycols such as ethylene glycol, 1,6-hexanediol,Bisphenol A, and the like, or other higher polyols such astrimethylolpropane, pentaerythritol, and the like. Polyols of higherfunctionality which can be utilized as indicated can be made, forinstance, by oxyalkylation of compounds such as sucrose or sorbitol. Onecommonly utilized oxyalkylation method is reaction of a polyol with analkylene oxide, for example, propylene or ethylene oxide, in thepresence of an acidic or basic catalyst. Specific examples of polyethersinclude those sold under the names TERATHANE and TERACOL, available fromE. I. Du Pont de Nemours and Company, Inc.

Polyepoxides such as those described below with reference to the curingagent (described below), can also be used.

In one particular embodiment of the present invention, the resinousbinder (i) comprises a polyurethane polymer having a number averagemolecular weight (Mn) of at least 2000. The number average molecularweight of the polyurethane polymer can range from 2000 to 500,000,typically from 3000 to 200,000.

The film-forming polymer can be present in the basecoating compositionsin an amount of at least 2 percent by weight, usually at least 5 percentby weight, and typically at least 10 percent by weight based on weightof total resin solids in the basecoating composition. Also, the polymerhaving reactive functional groups can be present in the basecoatingcompositions of the invention in an amount less than 80 percent byweight, usually less than 60 percent by weight, and typically less than50 percent by weight based on weight of total resin solids in thecoating composition. The amount of the film-forming polymer present inthe basecoating compositions of the present invention can range betweenany combination of these values inclusive of the recited values.

As aforementioned, in addition to the functional group-containingpolymer, the basecoating compositions used in the processes of thepresent invention can further comprise at least one curing agent havingfunctional groups reactive with the functional groups of the polymer.

Dependent upon the reactive functional groups of the film-formingpolymer, this curing agent can be selected from an aminoplast resin, apolyisocyanate, a blocked isocyanate, a polyepoxide, a polyacid, ananhydride, an amine, a polyol, and mixtures of any of the foregoing. Inone embodiment, the at least one curing agent is selected from anaminoplast resin and a polyisocyanate.

Aminoplast resins, which can comprise phenoplasts, as curing agents forhydroxyl, carboxylic acid, and carbamate functional group-containingmaterials are well known in the art. Suitable aminoplast resins, suchas, for example, those discussed above, are known to those of ordinaryskill in the art. Aminoplasts can be obtained from the condensationreaction of formaldehyde with an amine or amide. Non-limiting examplesof amines or amides include melamine, urea, or benzoguanamine.Condensates with other amines or amides can be used; for example,aldehyde condensates of glycoluril, which give a high meltingcrystalline product useful in powder coatings. While the aldehyde usedis most often formaldehyde, other aldehydes such as acetaldehyde,crotonaldehyde, and benzaldehyde can be used.

The aminoplast resin contains imino and methylol groups and in certaininstances at least a portion of the methylol groups are etherified withan alcohol to modify the cure response. Any monohydric alcohol can beemployed for this purpose including methanol, ethanol, n-butyl alcohol,isobutanol, and hexanol.

Non-limiting examples of aminoplasts include melamine-, urea-, orbenzoguanamine-formaldehyde condensates, in certain instances monomericand at least partially etherified with one or more alcohols containingfrom one to four carbon atoms. Non-limiting examples of suitableaminoplast resins are commercially available, for example, from CytecIndustries, Inc. under the trademark CYMEL® and from Solutia, Inc. underthe trademark RESIMENE®.

In yet another embodiment of the present invention, the curing agentcomprises a polyisocyanate curing agent. As used herein, the term“polyisocyanate” is intended to include blocked (or capped) isocyanatesas well as unblocked (poly) isocyanates. The polyisocyanate can be analiphatic or an aromatic polyisocyanate, or a mixture of the foregoingtwo. Diisocyanates can be used, although higher polyisocyanates such asisocyanurates of diisocyanates are often used. Higher polyisocyanatesalso can be used in combination with diisocyanates. Isocyanateprepolymers, for example, reaction products of polyisocyanates withpolyols also can be used. Mixtures of polyisocyanate curing agents canbe used.

If the polyisocyanate is blocked or capped, any suitable aliphatic,cycloaliphatic, or aromatic alkyl monoalcohol known to those skilled inthe art can be used as a capping agent for the polyisocyanate. Othersuitable capping agents include oximes and lactams. When used, thepolyisocyanate curing agent is typically present, when added to theother components which form the coating composition, in an amountranging from 0.5 to 65 weight percent, can be present in an amountranging from 10 to 45 weight percent, and often are present in an amountranging from 15 to 40 percent by weight based on the total weight ofresin solids present in the composition.

Other useful curing agents comprise blocked isocyanate compounds suchas, for example, the tricarbamoyl triazine compounds described in detailin U.S. Pat. No. 5,084,541, which is incorporated by reference herein.When used, the blocked polyisocyanate curing agent can be present, whenadded to the other components in the composition, in an amount rangingup to 20 weight percent, and can be present in an amount ranging from 1to 20 weight percent, based on the total weight of resin solids presentin the composition.

Anhydrides as curing agents for hydroxyl functional group-containingmaterials also are well known in the art and can be used in thebasecoating compositions of the present invention. Non-limiting examplesof anhydrides suitable for use as curing agents in the compositions ofthe invention include those having at least two carboxylic acidanhydride groups per molecule which are derived from a mixture ofmonomers comprising an ethylenically unsaturated carboxylic acidanhydride and at least one vinyl co-monomer, for example, styrene,alpha-methyl styrene, vinyl toluene, and the like. Non-limiting examplesof suitable ethylenically unsaturated carboxylic acid anhydrides includemaleic anhydride, citraconic anhydride, and itaconic anhydride.Alternatively, the anhydride can be an anhydride adduct of a dienepolymer such as maleinized polybutadiene or a maleinized copolymer ofbutadiene, for example, a butadiene/styrene copolymer. These and othersuitable anhydride curing agents are described in U.S. Pat. No.4,798,746 at column 10, lines 16-50; and in U.S. Pat. No. 4,732,790 atcolumn 3, lines 41-57, both of which are incorporated herein byreference.

Polyepoxides as curing agents for carboxylic acid functionalgroup-containing materials are well known in the art. Non-limitingexamples of polyepoxides suitable for use in the compositions of thepresent invention comprise polyglycidyl esters (such as acrylics fromglycidyl methacrylate), polyglycidyl ethers of polyhydric phenols and ofaliphatic alcohols, which can be prepared by etherification of thepolyhydric phenol, or aliphatic alcohol with an epihalohydrin such asepichlorohydrin in the presence of alkali. These and other suitablepolyepoxides are described in U.S. Pat. No. 4,681,811 at column 5, lines33 to 58, which is incorporated herein by reference.

Suitable curing agents for epoxy functional group-containing materialscomprise polyacid curing agents, such as the acid group-containingacrylic polymers prepared from an ethylenically unsaturated monomercontaining at least one carboxylic acid group and at least oneethylenically unsaturated monomer which is free from carboxylic acidgroups. Such acid functional acrylic polymers can have an acid numberranging from 30 to 150. Acid functional group-containing polyesters canbe used as well. The above-described polyacid curing agents aredescribed in further detail in U.S. Pat. No. 4,681,811 at column 6, line45 to column 9, line 54, which is incorporated herein by reference.

Also well known in the art as curing agents for isocyanate functionalgroup-containing materials are polyols, that is, materials having two ormore hydroxyl groups per molecule, different from component (b) whencomponent (b) is a polyol. Non-limiting examples of such materialssuitable for use in the compositions of the invention includepolyalkylene ether polyols, including thio ethers; polyester polyols,including polyhydroxy polyesteramides; and hydroxyl-containingpolycaprolactones and hydroxy-containing acrylic copolymers. Also usefulare polyether polyols formed from the oxyalkylation of various polyols,for example, glycols such as ethylene glycol, 1,6-hexanediol, BisphenolA and the like, or higher polyols such as trimethylolpropane,pentaerythritol, and the like. Polyester polyols also can be used. Theseand other suitable polyol curing agents are described in U.S. Pat. No.4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 tocolumn 9, line 66; and U.S. Pat. No. 3,919,315 at column 2, line 64 tocolumn 3, line 33, both of which are incorporated herein by reference.

Polyamines also can be used as curing agents for isocyanate functionalgroup-containing materials. Non-limiting examples of suitable polyaminecuring agents include primary or secondary diamines or polyamines inwhich the radicals attached to the nitrogen atoms can be saturated orunsaturated, aliphatic, alicyclic, aromatic,aromatic-substituted-aliphatic, aliphatic-substituted-aromatic, andheterocyclic. Non-limiting examples of suitable aliphatic and alicyclicdiamines include 1,2-ethylene diamine, 1,2-propylene diamine, 1,8-octanediamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like.Non-limiting examples of suitable aromatic diamines include phenylenediamines and the toluene diamines, for example, o-phenylene diamine andp-tolylene diamine. These and other suitable polyamines described indetail in U.S. Pat. No. 4,046,729 at column 6, line 61 to column 7, line26, which is incorporated herein by reference.

When desired, appropriate mixtures of curing agents may be used. Itshould be mentioned that the basecoating compositions can be formulatedas a one-component composition where a curing agent such as anaminoplast resin and/or a blocked isocyanate compound such as thosedescribed above is admixed with other composition components. Theone-component composition can be storage stable as formulated.Alternatively, compositions can be formulated as a two-componentcomposition, for example, where a polyisocyanate curing agent such asthose described above can be added to a pre-formed admixture of theother composition components just prior to application. The pre-formedadmixture can comprise curing agents such as aminoplast resins and/orblocked isocyanate compounds such as those described above.

As previously mentioned, the basecoating compositions useful in theprocesses of the present invention further comprise (ii) a pigmentcomposition. The pigment composition (ii) can include filler pigments,for example, talc and calcium carbonate; color-enhancing pigments, forexample, inorganic pigments such as titanium dioxide, red and black ironoxides, chromium oxide, lead chromate, and carbon black, and/or organicpigments such as phthalocyanine blue and phthalocyanine green; andeffect-enhancing pigments, for example, metallic pigments such asaluminum flake, copper or bronze flake, and metal oxide coated micaceouspigments. Any of the basecoating compositions used in the processes ofthe present invention can comprise one or more filler pigments,color-enhancing pigments, and/or effect-enhancing pigments, andcombinations thereof.

In another embodiment of the present invention, the basecoatingcompositions useful in the processes of the present invention furthercomprise an aqueous dispersion of polymeric microparticles, typicallycrosslinked polymeric microparticles. Such crosslinked microparticlescan be prepared, for example, the non-aqueous dispersion methodcomprising polymerizing a mixture of ethylenically unsaturatedco-monomers at least one of which is a crosslinking co-monomer, in anorganic liquid in which the mixture is soluble but the resultant polymeris insoluble. Most often, the polymeric microparticles used in thebasecoating compositions of the present invention can be prepared byemulsion polymerization of a mixture of ethylenically unsaturatedco-monomers which can include a crosslinkable monomer in an aqueousmedium by methods well known in the art. The ethylenically unsaturatedco-monomers can be polymerized in the presence of a polymer, typically ahydrophobic polymer, for example a hydrophobic acrylic, polyester,and/or a polyurethane polymer. By “crosslinkable monomer” is meant apolymerizable ethylenically monomer having at least two polymerizableethylenically unsaturated bonds in the molecule, or, alternatively, acombination of two different monomers having mutually reactive groups.Specific examples of such crosslinkable monomers include ethylene glycoldi(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, divinyl benzene, and a combination of an epoxyfunctional monomer such as glycidyl(meth)acrylate and a carboxylic acidfunctional monomer such as (meth)acrylic acid. Suitable, butnon-limiting examples of polymeric microparticles are those described inU.S. Pat. Nos. 5,071,904; 4,728,545; 4,539,363; and 4,403,003.

The first and/or second basecoating compositions useful in the processesof the present invention can comprise one or more aqueous dispersions ofpolymeric microparticles, usually crosslinked polymeric microparticles,in an amount up to 75 weight percent, sometimes up to 70 weight percent,sometimes up to 60 weight percent, and sometimes up to 55. Thebasecoating compositions also can comprise one or more aqueousdispersions of polymicroparticles, usually crosslinked polymericmicroparticles, in an amount equal to or greater than 20 weight percent,sometimes equal to or greater than 25 weight percent, sometimes equal toor greater than 30 weight percent, and sometimes equal to or greaterthan 35 weight percent. The amount of aqueous dispersion of polymericmicroparticles present in the basecoating compositions useful in theprocesses of the present invention, can range between any of theabove-stated levels, inclusive of the recited values.

In addition to the components described above, any of the basecoatingcompositions used in the processes of the present invention can containa variety of other optional ingredients. If desired, other resinousmaterials can be included in conjunction with the aforedescribedpolymers, curing agents and aqueous polymeric microparticles so long asthe resultant multilayer composite coating is not detrimentally affectedin terms of physical performance and appearance properties. Likewise thebasecoating composition can include additive materials, for example,rheology control agents, hindered amine light stabilizers and/orultraviolet light absorbers, catalysts, fillers, surfactants and thelike.

Once the basecoating composition has been applied directly onto at leasta portion of the electrodeposition coating layer to form a basecoatinglayer thereon, the basecoating layer, optionally, is dehydrated,typically by heating to a temperature and for a time sufficient to driveoff excess solvents, for example, water, but insufficient to cure thebasecoating layer. Dehydration of the basecoating layer also can beaccomplished by giving the basecoated substrate a flash period atambient conditions to for a time sufficient to allow solvent toevaporate from the coating layer. Suitable dehydration conditions willdepend on the particular basecoating and top coating compositionsemployed and on the ambient humidity, but in general, a dehydration timeof from 1 to 5 minutes at a temperature of 80° F. to 250° F. (20° C. to121.degree. C.) is sufficient. If a flash period is used in lieu of orin combination with thermal dehydration conditions, the basecoatinglayer can be exposed to ambient conditions for a period of from 1 to 20minutes.

The process further comprises forming a top coating layer on thebasecoating layer by depositing a curable top coating composition whichis substantially pigment-free directly onto at least a portion of theuncured basecoating layer (in a wet-on-wet application). Thesubstantially pigment-free top coating compositions used in any of theprocesses of the present invention can include aqueous coatingcompositions, solvent-based compositions, and compositions in solidparticulate form, i.e., powder coating compositions. Any of thetransparent or clear coating compositions known in the art are suitablefor this purpose. Suitable non-limiting examples include the clearcoating compositions described in U.S. Pat. Nos. 4,650,718; 5,814,410;5,891,981; and WO 98/14379. Specific non-limiting examples includeTKU-1050AR, ODCT8000, and those available under the tradenames DIAMONDCOAT® and NCT® all commercially available from PPG Industries, Inc.

As used herein, by “substantially pigment-free” coating composition ismeant a coating composition which forms a transparent coating, such as aclearcoat. Such compositions are sufficiently free of pigment orparticles such that the optical properties of the resultant coatings arenot seriously compromised. As used herein, “transparent” means that thecured coating has a BYK Haze index of less than 50 as measured using aBYK/Haze Gloss instrument.

Once the top coating layer (i.e., the clearcoating layer) has beenformed on at least a portion of the basecoating layer, the coatedsubstrate is subjected to conditions sufficient to simultaneously curethe top coating layer, the basecoating layer, and, optionally, theelectrodeposition layer. In the curing operation, solvents are drivenoff and the film-forming materials of the various coating layers areeach crosslinked. Curing of the coating layers can be accomplished byany known curing methods including by thermal energy, infrared, ionizingor actinic radiation, or by any combination thereof. Generally, thecuring operation can be carried out at temperatures ranging from 50° F.to 475° F. (10° C. to 246° C.), however, lower or higher temperaturesmay be used as necessary to activate crosslinking mechanisms. Cure is asdefined above.

In another embodiment, the present invention is directed to a processfor forming a multilayer composite coating on a substrate, the processcomprising: forming a first basecoating layer over the substrate bydepositing an aqueous curable first basecoating composition over atleast a portion of the substrate, optionally, dehydrating the firstbasecoating layer, forming a second basecoating layer over the firstbasecoating layer by depositing an aqueous curable second basecoatingcomposition, which is the same or different from the first basecoatingcomposition, directly onto at least a portion of the first basecoatinglayer, optionally, dehydrating the second basecoating layer, forming atop coating layer over the second basecoating layer by depositing acurable top coating composition which is substantially pigment-freedirectly onto at least a portion of the second basecoating layer; andcuring the top coating layer, the second basecoating layer, and thefirst basecoating layer simultaneously.

In this embodiment, the first basecoating composition can be applieddirectly onto the substrate surface of a non-metallic substrate or ametallic substrate with no intervening electrodeposition coating layer.That is, the first basecoating composition can be applied directly tothe “bare metal” surface of a metallic substrate (as described above) orto a metallic substrate to which a pretreatment or weldable primercoating composition has previously applied (as described above withreference to application of the electrodepositable coating composition).It also should be understood that for purposes of this embodiment,applying the first basecoating composition “over at least a portion ofthe substrate” does not preclude the previous application and optionalcuring of an electrodepositable coating composition over at least aportion of the substrate prior to application of the first basecoatingcomposition.

As aforementioned, the substrate also can comprise a non-metallicsubstrate, for example, an “elastomeric” substrate. Suitable elastomericsubstrates can include any of the thermoplastic or thermoset syntheticmaterials well known in the art. Non-limiting examples of suitableflexible elastomeric substrate materials include polyethylene,polypropylene, thermoplastic polyolefin (“TPO”), reaction injectedmolded polyurethane (“RIM”) and thermoplastic polyurethane (“TPU”).

Non-limiting examples of thermoset materials useful as substrates inconnection with the present invention include polyesters, epoxides,phenolics, polyurethanes such as “RIM” thermoset materials, and mixturesof any of the foregoing. Non-limiting examples of suitable thermoplasticmaterials include thermoplastic polyolefins such as polyethylene,polypropylene, polyamides such as nylon, thermoplastic polyurethanes,thermoplastic polyesters, acrylic polymers, vinyl polymers,polycarbonates, acrylonitrile-butadiene-styrene (“ABS”) copolymers,ethylene propylene diene terpolymer (“EPDM”) rubber, copolymers, andmixtures of any of the foregoing.

If desired, the elastomeric substrates described above can have anadhesion promoter present on the surface of the substrate over which anyof a number of coating compositions (including the coating compositionsof the present invention as described below) can be applied. Tofacilitate adhesion of organic coatings to such polymeric substrates,the substrate can be pretreated using an adhesion promoter layer or tiecoat, e.g., a thin layer 0.25 mils (6.35 microns) thick, or by flame orcorona pretreatment.

Suitable adhesion promoters for use over polymeric substrates includechlorinated polyolefin adhesion promoters such as are described in U.S.Pat. Nos. 4,997,882; 5,319,032; and 5,397,602, incorporated by referenceherein. Other useful adhesion promoting coatings are disclosed in U.S.Pat. No. 6,001,469 (a coating composition containing a saturatedpolyhydroxylated polydiene polymer having terminal hydroxyl groups),U.S. Pat. No. 5,863,646 (a coating composition having a blend of asaturated polyhydroxylated polydiene polymer and a chlorinatedpolyolefin) and U.S. Pat. No. 5,135,984 (a coating composition having anadhesion promoting material obtained by reacting a chlorinatedpolyolefin, maleic acid anhydride, acryl or methacryl modifiedhydrogenated polybutadiene containing at least one acryloyl group ormethacryloyl group per unit molecule, and organic peroxide), which areincorporated herein by reference.

When the substrates are used as components to fabricate motor vehicles(including, but not limited to, automobiles, trucks and tractors) theycan have any shape, and can be selected from the metallic and/ornon-metallic substrates described above. Typical shapes of automotivebody components can include body side moldings, fenders, bumpers, hoods,and trim for automotive vehicles.

In any of the processes of the present invention, the second basecoatingcomposition can be the same or different from the first basecoatingcomposition. The second basecoating composition comprises (i) a secondresinous binder composition and (ii) a second pigment compositiondispersed in the second resinous binder. The second resinous bindercomposition can be the same or different from the first resinous bindercomposition; and, likewise, the second pigment composition can be thesame or different from the first pigment composition.

The second resinous binder composition can comprise a film-formingpolymer selected from an acrylic polymer, a polyester polymer, apolyurethane polymer, a polyether polymer, a polyepoxide polymer, asilicon-containing polymer, mixtures thereof, and copolymers thereof,such as those described above in detail with reference to the firstresinous binder composition. In one embodiment of the present invention,the first resinous binder composition and the second resinous bindercomposition comprise the same or different polyurethane polymer (such asany of the above-described polyurethane polymers). In an alternativeembodiment, the first resinous binder composition and the secondresinous binder composition comprise the same or different polyurethanepolymer, wherein the concentration of the polyurethane polymer in thefirst basecoating composition is less than or equal to the concentrationof the polyurethane polymer present in the second basecoatingcomposition, where concentrations are based on total resin solidspresent in the basecoating compositions.

As previously mentioned, in any of the processes of the presentinvention where both first and second basecoating compositions areemployed, the second pigment composition can be the same or differentfrom the first pigment composition. The second pigment composition cancomprise any of the filler pigments, color-enhancing pigments and/oreffect-enhancing pigments described in detail above with respect to thefirst pigment composition. In one embodiment, the second basecoatingcomposition comprises color-enhancing and/or effect enhancing pigments.

In a further embodiment, the present invention is directed to a processfor forming a multilayer composite coating on any of the previouslydescribed metallic substrates, the process comprising: forming anelectrodeposition coating layer on the substrate by electrodeposition ofa curable electrodepositable coating composition, such as any of theabove-described electrodepositable coating compositions, over at least aportion of the substrate; optionally, heating the coated substrate to atemperature and for a time sufficient to cure the electrodeposiitoncoating layer; forming a first basecoating layer over theelectrodeposition coating layer by depositing an aqueous curable firstbasecoating composition (such as any of the basecoating compositionsdescribed above) directly onto at least a portion of theelectrodeposition coating layer, optionally, dehydrating the firstbasecoating layer; forming a second basecoating layer over the firstbasecoating layer by depositing an aqueous curable second basecoatingcomposition (such as any of the basecoating compositions describedabove), which is the same or different from the first basecoatingcomposition, directly onto at least a portion of the first basecoatinglayer, optionally, dehydrating the second basecoating layer; forming atop coating layer over the second basecoating layer by depositing acurable top coating composition (such as any of the clear coatingcompositions described above) which is substantially pigment-freedirectly onto at least a portion of the second basecoating layer; andcuring the top coating layer, the second basecoating layer, the firstbasecoating layer, and, optionally, the electrodeposition coating layersimultaneously.

The first and second basecoating compositions, or in instances where thebasecoating composition is used to form only one basecoating layer overa metal substrate or directly onto an electrodeposition coating layer,have a pigment to binder ratio based on solids content ranging 0.1 to4.0:1, usually from 0.1 to 3.0:1, and typically from 0.1 to 2.0:1. Itshould be understood that the pigment to binder ratio of the basecoatingcomposition can vary widely dependent upon the composition, the pigmenttype, and/or the color desired.

Also, the film thickness of the cured first and second basecoatinglayers (or, alternatively, the sole basecoating layer where applicable)can range from 1 to 50, usually from 5 to 30, and often from 10 to 25micrometers. Likewise, it should be understood that the film thicknessof the cured basecoating layer can vary widely dependent upon thebasecoating composition as well as the basecoat color or pigmentation.

In any of the processes of the present invention where first and secondbasecoating compositions are employed, the first and second basecoatinglayers can be color-harmonized. That is, despite compositionaldifferences in resinous binder and/or pigment compositions (if suchcompositional differences exist), the first and second basecoatinglayers when cured are sufficiently similar in color that the curedsecond basecoating layer can have a film thickness significantly lessthan that of the cured first basecoating layer without deleteriouslyeffecting appearance properties of the multilayer composite coating.

In another embodiment of the present invention, the cured firstbasecoating layer (or, alternatively, the sole basecoating layer whereapplicable) has 5 percent or less light transmission as measured at 400nanometers at a film thickness of 15 micrometers. For purposes of thepresent invention, the percent light transmission is determined bymeasuring light transmission of free cured basecoat films ranging from14 to 16 micrometers film thickness, using a Perkin-Elmer Lambda 9scanning spectrophotometer with a 150 millimeter Lap Sphere integratingsphere. Data is collected using Perkin-Elmer UV WinLab software inaccordance with ASTM E903, Standard Test Method for Solar Absorbance,Reflectance, and Transmittance of Materials Using Integrating Spheres.

In any of the processes of the present invention which comprise thesequential steps of applying any of the aforedescribed first basecoatingcompositions over the substrate or, alternatively, directly onto atleast a portion of the electrodeposition coating layer, to form a firstbasecoating layer thereon; optionally, dehydrating the first basecoatinglayer; and applying any of the aforedescribed second basecoatingcompositions, which are different from the first basecoatingcomposition, directly onto the first basecoating layer to form a secondbasecoating layer thereon, the first basecoating composition can furthercomprise a composition comprising the second pigment compositiondispersed in the second resinous binder. The composition comprising thesecond pigment composition dispersed in the second resinous binder canbe admixed with the first basecoating composition immediately prior todeposition of the first basecoating composition over the substrate or,alternatively, directly onto the electrodeposition coating layer. Inthis embodiment, it should be understood that the “compositioncomprising the second pigment composition dispersed in the secondresinous binder” can include any of the fully formulated secondbasecoating compositions, or, alternatively, a pigment paste compositionwhich comprises the second pigment composition dispersed in a secondresinous binder comprising a polymer, for example a grind vehicle. Itshould also be understood that in this embodiment, the first basecoatinglayer can be formed from a first basecoating composition which comprisesa greater proportion of the first basecoating composition with which hasbeen admixed a smaller proportion of the second basecoating composition,or vice versa.

Additionally, in one embodiment of the invention the first and/or secondbasecoat compositions can be formed by dynamically mixing selectedcomponents of the basecoat compositions. Further, the basecoatcomposition applied in the cut-in station can be formed by dynamicallymixing the first and second basecoat compositions. Suitable dynamicmixing apparatus and methods are described in U.S. Pat. Nos. 6,291,018and 6,296,706, which are herein incorporated by reference in theirentirety.

In yet a further embodiment of the present invention, any of thepreviously described basecoating compositions can be applied over atleast a portion of a substrate, or alternatively, directly onto at leasta portion of a previously formed electrodeposition coating layer (asdescribed above), to form a single basecoating layer thereon;optionally, the basecoating layer is dehydrated but not cured; asubstantially pigment-free top coating composition (such as any of thepreviously applied clear coating compositions) is applied directly ontoat least a portion of the basecoating layer to form a clear top coatinglayer thereon; and the coated substrate is subjected to conditionssufficient to cure the top coat layer, the basecoat layer, and,optionally, the electrodeposition layer. In this embodiment, the topcoating composition is applied directly onto one basecoating layer in awet-on-wet application.

The processes of the present invention provide multilayer compositecoatings which have excellent appearance and physical properties, andare particularly suitable for use in the coating of motor vehicles, forexample, automobiles and trucks. In a particular embodiment, themultilayer composite coating formed by any of the processes of thepresent invention described herein has a chip resistance rating rangingfrom 4 to 10, typically from 6 to 10, as determined in accordance withASTM D 3170-01.

The present invention also is directed to an improved process forforming a multilayer composite coating on a motor vehicle substratecomprising the sequential steps of:

(1) passing a conductive motor vehicle substrate to an electrocoatingstation located on a coating line;

(2) electrocoating the substrate serving as a charged electrode in anelectrical circuit comprising said electrode and an oppositely chargedcounter electrode, said electrodes being immersed in an aqueouselectrodepositable composition (such as any of the previously describedelectrodepositable coating compositions), comprising passing electriccurrent between said electrodes to cause deposition of theelectrodepositable composition on the substrate as a substantiallycontinuous film of electrodeposition coating;

(3) passing the coated substrate of step (2) through anelectrodeposition coating curing station located on the coating line tocure the electrodepositable composition on the substrate, forming anelectrodeposition coating layer thereon;

(4) passing the coated substrate of step (3) to a primer-surfacercoating station located on the coating line;

(5) applying a primer-surfacer coating composition directly to at leasta portion of the electrodeposition coating layer to form aprimer-surfacer coating layer thereon;

(6) passing the coated substrate of step (5) through a primer-surfacercuring station located on the coating line to cure the primer-surfacercoating layer;

(7) passing the coated substrate of step (6) to a basecoating stationlocated on the coating line;

(8) applying an aqueous basecoating composition directly onto at least aportion of the primer-surfacer coating layer to form a basecoating layerthereon;

(9) optionally, passing the coated substrate of step (8) through a flashoven located on the coating line to dehydrate but not cure thebasecoating layer; (10) passing the coating substrate of step (8), oroptionally step (9), to a clearcoating station located on the coatingline;

(11) applying a substantially pigment-free coating composition (such asany of the previously described transparent or clear coatingcompositions) directly onto at least a portion of the basecoating layerto form a clearcoating layer thereon; and

(12) passing the coating substrate of step (11) through a topcoatingcuring station located on the coating line to cure the basecoating layerand the clearcoating layer simultaneously. The improvement comprisespassing the coated substrate of step (3) directly to a basecoatingstation located a coating line, sequentially applying in a wet-on-wetapplication, separate, multiple aqueous basecoating compositions (suchas any of the previously described basecoating compositions) directlyonto at least a portion of the electrodeposition coating layer,optionally, dehydrating each successive basecoating composition, to forma multilayer basecoating thereon, with no intervening primer-surfacercoating layer between the electrodeposition coating layer and themultilayer basecoating, passing the coated substrate to a clearcoatingstation located on the coating line, applying a substantiallypigment-free coating composition (for example, any of the previouslydescribed clear coating compositions) directly onto at least a portionof the multilayer basecoating to form a clearcoating layer thereon, andpassing the coated substrate through a topcoating curing station locatedin the curing line to cure the multilayer basecoating and theclearcoating layer simultaneously.

The invention is also directed to a coating line comprising anelectrocoating zone including at least one electrodeposition bath. Abasecoat is zone located downstream of and adjacent to theelectrocoating zone, the basecoat zone comprising a cut-in station, afirst basecoat station, and a second basecoat station. A topcoat zone islocated downstream of and adjacent to the basecoat zone.

Illustrating the invention are the following examples which, however,are not to be considered as limiting the invention to their details. Allparts and percentages in the following examples as well as throughoutthe specification are by weight unless otherwise indicated.

EXAMPLES

The following examples illustrate the processes of the presentinvention. Example A describes the preparation of a medium gray firstbasecoating composition. Comparative Process Example 1 describes theapplication (in two coats) of a conventional silver metallic basecoatcomposition to a cured electrocoat primer, followed by application of aclear coating composition. Process Example 2 describes the process ofthe present invention wherein the first basecoating composition ofExample A is applied to the cured electrocoat primer, followed byapplication of the conventional silver metallic basecoat and subsequentapplication of the clear coating composition. Examples B through Edescribe the preparation of basecoating compositions analogous to thatof Example A, but having varying levels of the waterborne polyurethaneresin.

Example A

This example describes the preparation of a medium gray base coatcomposition suitable as the first basecoating composition used to formthe first basecoating layer in the process of the present invention. Thefirst basecoating composition was prepared by admixing the followingingredients under mild agitation.

INGREDIENTS: Total Weight (Grams) N-butoxy propanol 15.00 1-octanol 5.00CYMEL 327¹ 22.22 Phosphatized epoxy resin² 1.63 TINUVIN 1130³ 3.00Deionized water 10.00 Odorless mineral spirits⁴ 8.00 Acrylic-polyesterlatex⁵ 41.07 Waterborne polyurethane resin⁶ 39.23 Titanium dioxidepaste⁷ 148.76 Carbon black paste⁸ 25.60 SETALUX 6802 AQ-24⁹ 118.75Dimethyl ethanolamine¹⁰ 2.86 Deionized water 37.56 ¹Methoxymethyl iminofunctional melamine-formaldehyde resin available from CYTEC Industries,Inc. ²Phosphatized epoxy prepared by reacting EPON 880 (polyglycidylether of Bisphenol A available from Shell Chemicals) with phosphoricacid in an 83:17 ratio. ³Ultraviolet light stabilizer available fromCiba Specialty Chemicals, Inc. ⁴Available from Shell Oil and ChemicalCo. ⁵Latex prepared from 70.6% polyester-acrylic (52.8% 1,6-hexanediol,27.2% isophthalic acid, 10% adipic acid, 10% maleic anhydride in 66.7%butyl acrylate/33.3% hydroxypropyl methacrylate), 2.4% ethylene glycoldimethacrylate, 20% styrene, 4.7% hydroxypropyl methacrylate, 2.3%acrylic acid, having a solids content of 45% by weight. ⁶Polyurethaneresin prepared from 53.8% POLYMEG 2000 (available from BASF), 23.9%isophorone diisocyanate, 6.4% dimethylolpropionic acid, 3.2% adipic aciddihydrazide, 12.7% polyester (54.2% EMPOL 1008 (available fromCOGNIS-EMERY Group), 29.8% 1,6-hexanediol, 16.1% isophthalic acid, andhaving a solids content of 39% by weight. ⁷Rutile titanium dioxide(available from E. I. DuPont de Nemours and Company as R 900-39)dispersed in a resin blend of 37.0% waterborne acrylic resin (8.5%hydroxyethyl acrylate, 18.0% butyl methacrylate, 30.0% styrene, 35.0%butyl acrylate, 8.5% acrylic acid made at 27.0% solids), 38.4%acrylic-polyester-urethane latex [3.0% ethylene glycol dimethacrylate,11.0% methyl methacrylate, 24% butyl acrylate, 2% acrylic acid, and 60%polyester-acrylic-urethane (neopentyl glycol, adipic acid, hydroxyethylacrylate-butyl acrylate, 1,6-hexamethylene diisocyanate) made at 43.5%solids], and 24.6% polypropylene glycol 425. The dispersion has a 69.5%weight solids content and a pigment to binder ratio of 6.71. ⁸MONARCH1300 carbon black pigment (available from Cabot) dispersed in 100%aqueous acrylic resin. The dispersion has a 24.1% weight solids contentand a pigment to binder ratio of 0.35. ⁹Waterborne acrylic rheologycontrol agent available from Akzo Nobel. This material is supplied at aresin solids content of 24%. ¹⁰50% dimethyl ethanolamine in deionizedwater.

The first basecoating composition of Example A was prepared as describedabove to provide a composition having a weight solids content of 40.9%;a pigment to binder ratio of 0.91; a pH of 8.68; and a #4 DIN Cupviscosity of 35.6 seconds at room temperature.

Comparative Process 1

A conventional silver metallic aqueous basecoat (available from PPG asNHWB-300146) was spray-applied in two coats to coated steel substrate(cold rolled steel B952 P60 D1 coated with PPG ED 5000 electrocoat,available from ACT). The resultant basecoat had a film thickness of 0.59mils (15 micrometers). Subsequent to application, the silver basecoatwas dehydrated for ten minutes at 176° F. (80° C.). A clear coatingcomposition (available from PPG Industries, Inc. as TKU-1050AR) was thenspray-applied to the dehydrated silver basecoat. The resultant clearcoat had a film thickness of 2.06 mils (52 micrometers). Afterapplication of the clear coating composition, the coated substrate wasgiven a room temperature flash period of ten minutes, and then heated toa temperature of 285° F. (140° C.) for thirty minutes.

Process 2

To illustrate the process of the present invention, the medium graybasecoating composition of Example A was spray-applied in one coat tocoated steel substrate (cold rolled steel B952 P60 D1 coated with PPG ED5000 electrocoat, available from ACT) to provide a film thickness of0.61 mils (15 micrometers). The coated substrate was then given a ninetysecond room temperature flash period. A conventional silver metallicaqueous basecoat (available from PPG as NHWB-300146) then wasspray-applied in one coat. The resultant silver basecoat had a filmthickness of 0.35 mils (9 micrometers). Subsequent to application, thesilver basecoat was dehydrated for ten minutes at 176° F. (80° C.). Aclear coating composition (available from PPG Industries, Inc. asTKU-1050AR) was then spray-applied to the dehydrated silver basecoat.The resultant clear coat had a film thickness of 1.97 mils (50micrometers). After application of the clear coating composition, thecoated substrate was given a room temperature flash period of tenminutes, then heated to a temperature of 285° F. (140° C.) for thirtyminutes.

The multilayer composite coatings prepared by the above-describedprocesses were tested as follows. The 20° specular gloss of theresultant multilayer composite coatings was measured using a NOVO GLOSSstatistical 20° glossmeter manufactured by GARDCO. Gloss results arereported in values ranging from 0 to 100, with a higher value indicatinghigher gloss.

The Dorigon Distinctness of Image (“DOI”) was measured using a DORIGONII meter manufactured by Hunter Lab. Higher values indicate better DOI.The long wave and short wave values are a measure of the coatingsurface, i.e., surface topography, smoothness. The BYK wavescan valuesreported below were measured using a BYK-Gardner WaveScan meter. Lowernumbers indicate a smoother surface.

Film hardness was measured using a Fischerscope H100 micro-hardnesstesting system manufactured by Fischer. The numbers are generated usingthe DIN 50359 standard method. Hardness values are reported inNewtons/mm² units. Higher values indicate a harder film. Aluminum flakeorientation, and thus change in reflectance with a change in viewingangle, was measured using an ALCOPE LMR-200 Laser Multiple Reflectometermanufactured by Alesco. A higher reported “FF” value indicates betteraluminum flake orientation.

Test results are presented in the following Table 1.

TABLE 1 Fischer BYK Wave Scan Micro- Aluminum 20° Dorigon Long ShortHarness Orientation Gloss DOI Wave Wave N/mm² FF Value Process 1* 90 902.2 13.9 145.7 1.65 Process 2 92 90 2.2 13.2 147.4 1.78 *Comparativeprocess.

The data presented in Table 1 above illustrate that the process forforming a multilayer composite coating of the present invention providesa multilayer composite coating having at least equivalent or improvedaluminum flake orientation.

Light transmittance of two respective multilayer composite coatingsformed by the Comparative Process 1 and the process of the presentinvention, Process 2, were compared as follows. Free films (nosteel/electrocoat substrate) were prepared using the respectiveprocesses. Coating systems (as described below) were applied to TEDLARsubstrates (available from Electrical Insulation Suppliers of Atlanta,Ga.). The free films then were peeled away from the TEDLAR substrate andthe percent light transmission was measured through the free paint. Thepercent transmission data measurements were made using a Perkin ElmerLambda 9 spectrophotometer with a 150 mm Labsphere integrating sphere inaccordance with ASTM E 903-82 “Standard Test Method for SolarAbsorptance, Reflectance, and Transmittance of Materials UsingIntegrating Spheres”. Perkin-Elmer UVWinLab software was used for datacollection.

The free film prepared using Comparative Process 1 included 0.59 mils(15 micrometers) of NHWB 300146 silver metallic basecoat; and 2.0 mils(51 micrometers) of TKU 1050AR clear coat. The free film prepared usingProcess 2 included 0.61 mils (15 micrometers) of the basecoatingcomposition of Example A; 0.35 mils (9 micrometers) of NHWB 300146silver metallic basecoat; and 1.98 mils (50 micrometers) of TKU 1050ARclear coat. The basecoating and clearcoating compositions were appliedand processed generally as described above. The percent lighttransmission for the respective multilayer coating systems measured atvarious wavelengths can be found in the following Table 2.

TABLE 2 % Light Transmission through Films at Various Wavelengths(nanometers) Wavelength (nm) 300 350 400 450 500 Process 1* 0 0 2.033.01 3.06 Process 2 0 0 0 0 0 *Comparative

The data presented in Table 2 above illustrate that the multilayercomposite coating prepared using the process of the present inventionexhibits 0% light transmission at all wavelengths evaluated, while thecomposite coating prepared by the comparative process exhibits lighttransmittance at wavelengths ranging from 400 to 500 nanometers. Itwould be understood by one skilled in the art that a low percent lighttransmittance can be related to improved exterior durability becauseless light reaches the under-layers of a multilayer coating system, suchas the less durable electrocoat layer, thereby causing coating layerdegradation such as by photo-oxidation.

Examples B-E

The following Examples B to E describe the preparation of medium graybasecoating compositions comprising varying levels polyurethane resin.The composition of Example B comprises 3.1% by weight solids of thepolyurethane; the composition of Example C comprises 10.6% by weightsolids of the polyurethane; the composition of Example D comprises 18.1by weight solids of the polyurethane; and the composition of Example Ecomprises 33.1% by weight solids of the polyurethane. The respectivebasecoating compositions were prepared by admixing the specifiedingredients under mild agitation.

Example B

INGREDIENTS Total Weight (Grams) N-butoxy propanol 15.00 1-Octanol 5.00CYMEL 327 22.22 Phosphatized epoxy resin of Example A 1.63 TINUVIN 11303.00 Odorless mineral spirits of Example A 8.00 Acrylic-polyester latexof Example A 74.53 Polyurethane resin of Example A 0 Titanium dioxidepaste of Example A 148.76 Carbon black paste of Example A 25.60 SETALUX6802 AQ-24 118.75 Dimethyl ethanolamine of Example A 3.46 Deionizedwater 63.51

The basecoating composition of Example B was prepared to have a 39.96%weight solids; a pigment to binder ratio of 0.92; a pH of 8.69; and a #4DIN cup viscosity of 34.6 seconds.

Example C

INGREDIENTS Total Weight (Grams) N-butoxy propanol 15.00 1-Octanol 5.00CYMEL 327 22.22 Phosphatized epoxy resin of Example A 1.63 TINUVIN 11303.00 Odorless mineral spirits of Example A 8.00 Acrylic-polyester latexof Example A 57.87 Polyurethane resin of Example A 19.23 Titaniumdioxide paste of Example A 148.76 Carbon black paste of Example A 25.60SETALUX 6802 AQ-24 118.75 Dimethyl ethanolamine of Example A 3.32Deionized water 62.85

The basecoating composition of Example C was prepared to have 39.82%weight solids; a pigment to binder ratio of 0.92; a pH of 8.70; and a #4DIN cup viscosity of 33.5 seconds.

Example D

INGREDIENTS Total Weight (Grams) N-butoxy propanol 15.00 1-Octanol 5.00CYMEL 327 22.22 Phosphatized epoxy resin of Example A 1.63 TINUVIN 11303.00 Odorless mineral spirits of Example A 8.00 Acrylic-polyester latexof Example A 41.20 Polyurethane resin of Example A 38.46 Titaniumdioxide paste of Example A 148.76 Carbon black paste of Example A 25.60SETALUX 6802 AQ-24 118.75 Dimethyl ethanolamine of Example A 3.05Deionized water 66.03

The basecoating composition of Example D was prepared to have 39.38%weight solids; a pigment to binder ratio of 0.92; a pH of 8.71; and a #4DIN cup viscosity of 32.6 seconds.

Example E

INGREDIENTS Total Weight (Grams) N-butoxy propanol 15.00 1-Octanol 5.00CYMEL 327 22.22 Phosphatized epoxy resin of Example A 1.63 TINUVIN 11303.00 Odorless mineral spirits of Example A 8.00 Acrylic-polyester latexof Example A 7.87 Polyurethane resin of Example A 76.92 Titanium dioxidepaste of Example A 148.76 Carbon black paste of Example A 25.60 SETALUX6802 AQ-24 118.75 Dimethyl ethanolamine of Example A 2.31 Deionizedwater 82.94

The basecoating composition of Example E was prepared to have 37.76%weight solids; a pigment to binder ratio of 0.92; a pH of 8.67; and a #4DIN cup viscosity of 26.0 seconds.

The data presented below in Tables 2 shows that the measured physicalproperties for the multi-layer coatings prepared from the basecoatingcompositions of Examples B to E described above. The coatings preparedusing Process 2 all provide appearance and chip resistance equivalent tocoatings made using standard Process 3.

TABLE 2 Film Thickness (mils) BYK Wave Scan Basecoat Process Base NHWBTKU 20° Long Short Chip Example # coat 300146 1050AR Gloss Wave WaveTest^(b) B 2 0.60 0.29 1.63 91 2.9 15.6 2 C 2 0.64 0.30 1.63 90 2.6 16.02 D 2 0.63 0.29 1.63 90 2.1 15.6 2 E 2 0.63 0.28 1.63 89 3.2 15.4 2 —  3^(a) — 0.67 1.63 92 3.5 18.0 2 ^(a)Process # 3 is the same as #1except for a change in substrate to ACT supplied cold rolled steel C710C18 DI coated with PPG ED 5000 Electrocoat and 1177225A gray primersurfacer available from PPG Industries, Inc. ^(b)The chip testing wasdone using the Stone Hammer Blow Testing Instrument Model 508manufactured by ERICHSEN GMBH & CO KG. Five hundred grams of fracturedsteel shot at 2 Bar Pressure was applied to each test panel twice. Avisual rating scale from DIN 55996-1 was used to rate the panels. TheKennwert rating scale is from 0.5 to 5 with lower values indicatingbetter resistance to chipping.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications which are within the spirit and scopeof the invention, as defined by the appended claims.

1. A process for forming a multilayer composite coating on a substrate,the process comprising: forming a first basecoating layer on thesubstrate by depositing an aqueous curable first basecoating compositionover at least a portion of the substrate with no interveningprimer-surfacer layer, optionally, dehydrating the first basecoatinglayer; forming a second basecoating layer on the first basecoating layerby depositing an aqueous curable second basecoating composition, whichis the same or different from the first basecoating composition,directly onto at least a portion of the first basecoating layer,optionally, dehydrating the second basecoating layer; forming a topcoating layer on the second basecoating layer by depositing a curabletop coating composition which is substantially pigment-free directlyonto at least a portion of the second basecoating layer; and curing thetop coating layer, the second basecoating layer, and the firstbasecoating layer simultaneously.
 2. The process of claim 1, wherein thesubstrate is a metallic substrate.
 3. The process of claim 2, whereinthe substrate is a non-metallic substrate.
 4. The process of claim 2,wherein the first basecoating composition is applied over a weldableprimer coating layer which had been previously applied over thesubstrate.
 5. The process of claim 4, wherein the weldable primercoating layer is formed by depositing a weldable primer coatingcomposition over the substrate, the weldable primer coating compositioncomprising: (A) a resinous binder comprising: (1) at least onefunctional group-containing polymer, and (2) at least one curing agenthaving functional groups reactive with the functional groups of (1); and(B) at least one electroconductive pigment dispersed in resinous binder(A).
 6. A coating line, comprising: an electrocoating zone including atleast one electrodeposition bath; a basecoat zone located downstream ofand adjacent to the electrocoating zone, the basecoat zone comprising acut-in station, a first basecoat station, and a second basecoat station;and a topcoat zone located downstream of and adjacent to the basecoatzone.
 7. The coating line of claim 6, wherein the cut-in station islocated upstream of the first basecoat station and the first basecoatstation is located upstream of the second basecoat station.
 8. Thecoating line of claim 6, wherein the first basecoat station includes atleast one bell applicator in flow communication with a source of a firstbasecoat composition comprising a first resinous binder and a firstpigment composition.
 9. The coating line of claim 8, wherein the secondbasecoat station includes at least one gun applicator in flowcommunication with a source of a second basecoat composition comprisinga second resinous binder and a second pigment composition, with thesecond pigment composition being different than the first pigmentcomposition.
 10. The coating line of claim 9, wherein the cut-in stationincludes at least one applicator in flow communication with a source ofthe second coating composition.
 11. The coating station of claim 9,wherein the cut-in station is in flow communication with a source of amixture of the first and second basecoat compositions.
 12. The coatingline of claim 6, wherein the basecoat zone further includes at least onedrying oven.
 13. The coating line of claim 6, wherein the cut-in stationis located downstream of the first basecoat station and/or the secondbasecoat station.
 14. The coating line of claim 6, wherein there is nodrying device positioned between the first and second basecoat stations.